Organometallic tin oxocarboxylate cluster with mixed organic ligands for EUV lithography

Abstract

The subject matter disclosed and claimed relates to Sn6-oxoclusters having mixed organic ligands and / or mixed carboxylate ligands, their synthesis, formulations thereof, and their use in EUV lithography.

Description

[Technical Field]

[0001] [Background technology]

[0002] field

[0003] The subject matter disclosed and claimed relates to Sn6-oxoclusters having mixed organic ligands, their synthesis, formulations thereof, and their use in EUV lithography.

[0004] Related technologies

[0005] Moore's Law continues to apply to the microelectronics industry. In photolithography, there is a tendency for smaller sizes to be better, and shorter wavelength light sources have come into use to manufacture high-density, high-performance semiconductor devices. For example, EUV (extreme ultraviolet) lithography uses short wavelengths of around 13.5 nm. However, because the output of EUV light sources is low, it is necessary to use highly sensitive EUV resist materials. Therefore, conventional chemically amplified photoresist systems used in conventional lithography have reached their limits because they have poor photon absorption in thin films, moderate etching selectivity, and resolution is limited by particle size.

[0006] The semiconductor industry is currently exploring the use of metal-containing materials as EUV photoresist materials for patterning. Many organometallic complexes, particularly tin-containing compounds, are being evaluated as candidate precursors for the formation of photoresist materials by either spin coating or chemical vapor deposition. Some of these inorganic photoresists have the potential to offer higher sensitivity, form thinner films, have greater etching resistance, reduce line edge roughness, and improve resolution.

[0007] Sn compounds / clusters are attracting attention as photoresists due to their mechanical strength and etching resistance as crosslinking materials. However, to function as a photoresist, excellent photosensitivity and optical resolution are required.

[0008] For example, U.S. Patent No. 10,787,466 discloses a composition of a monoalkyltin trialkoxide compound of formula RSn(OR')3 or a monoalkyltin triamide compound of formula RSn(NR'2)3, where (i) R is a hydrocarbyl group having 1 to 31 carbon atoms, and R' is a hydrocarbyl group having 1 to 10 carbon atoms; and (ii) the composition contains 4 mol% or less of the dialkyltin compound relative to the total amount of tin. A composition containing a monoalkyltriamide tin compound of formula RSn-(NR'COR'')3 is also disclosed, where R is a hydrocarbyl group having 1 to 31 carbon atoms, and R' and R'' are independently hydrocarbyl groups having 1 to 10 carbon atoms. It is believed that the presence of dialkyltin compounds (as impurities) in a formulation affects its performance.

[0009] International Publication No. 2019246254 discloses a precursor solution for radiation-patternable coatings formed using an organic solvent and a monoalkyltin trialkoxide. In this solution, the water content of the solvent is adjusted to within 10% of a selected value. Generally, the water content of the solvent is adjusted by adding water, but water can also be removed. For example, in some embodiments, the adjusted water content of the solvent can range from about 250 ppm by weight to about 10,000 ppm by weight. By selecting appropriate ligands, the adjusted precursor solution is claimed to be stable for at least about 42 days, and in some cases at least 8 months.

[0010] U.S. Patent No. 10,732,505 discloses organometallic precursors for forming high-resolution lithographic patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally comprise ligands that are readily hydrolyzable by steam or other -OH sources under mild conditions. In particular, the organometallic precursors comprise tin-radiosensitive organic ligands that can be effective for high-resolution patterning at relatively low radiation doses and can produce coatings particularly useful for EUV patterning.

[0011] U.S. Patent Application Publication 2021 / 0087210 describes the synthesis of Sn6 drum clusters having only nBu substituents with a single, narrowly defined type of carboxylate ligand (all carboxylate ligands in a single compound are the same), and their potential use as photoresists in EUV lithography processes. Due to the nature of the ligands used, the solubility of the compound is expected to be relatively poor, requiring the use of aromatic solvents such as toluene or xylene. These solvents pose significant health risks and are therefore unsuitable for industrial applications in IC manufacturing.

[0012] U.S. Patent Application Publication 2022 / 0365428 describes bisalkylSn clusters having two or more different carboxylate ligands and their use as photoresist materials in EUV lithography. This disclosure does not include compounds in which individual Sn atoms have different alkyl ligands. In general, bisalkylSn compounds are more toxic than their respective monoalkyl compounds. Therefore, when organotin compounds are required, monoalkyl compounds are a preferred choice.

[0013] Sn12 cluster (i.e., (RSn) 12 O 14[OH]6X2) is described as photosensitive to EUV and electron beam irradiation. See Sharps et al., Chem. Mater., 31, 4840-4850 (2019); U.S. Patent No. 9,310,684; Castellanos et al., Appl. Mat. Int., 12, 9881-9889 (2020); and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019). Changes in materials coated on wafers as a photosensitive layer have been investigated, and several hypotheses have been discussed regarding how solubility contrast is induced by exposure to ionizing radiation. See Castellanos et al., Appl. Mat. Int., 12, 9881-9889 (2020) and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019).

[0014] The subject matter disclosed and claimed is based on a functionalized Sn-6 drum cluster. Due to its high stability, the Sn6 drum cluster has the potential to be an attractive alternative to known Sn-based systems, and is expected to yield stable formulations and stable photoresist films. The Sn6 drum cluster contains a Sn6O6 core. This core motif consists of six (Sn2O2) four-membered rings that fuse along their edges to form a drum-like cyclic structure. Alternatively, the Sn6O6 core can also be described as two (Sn3O3) rings with Sn-O-Sn bonds. The two rings are aligned to rotate relative to each other, forming a drum-like motif as an effect of additional Sn-O-bridging between the rings. Each Sn atom has one organic substituent "R a Typically, it is covalently bonded to an alkyl or aryl group. Furthermore, it is bonded in a cross-linked structure to a carboxylate ligand "-O2C-R b These exist. They form a bond between two tin atoms in a six-membered ring. This arrangement gives specific orientation to different ligands. aAll groups are located on a six-membered ring, and the carboxylate residues face outward from the radial portion of the cluster core. For example, (nBuSn)6O6(O2CCH3)6 has the structure shown in Figure 14 (H atoms are not shown).

[0015] This type of cluster was first described by Chandrasekhar et al. (See Chandrasekhar et., Inorg. Chem., 24, 1970-1971 (1985)). Over the past several decades, various functionalized derivatives have been synthesized and applied to a wide range of uses, such as materials science or medicinal chemistry. In all cases, a single alkyl-Sn source, typically n-butyl stannoic acid, has been used as the starting material, and various types of carboxylic acids have been employed. In all experiments, clusters with a single type of alkyl group bonded to the tin atom were generated, and in all cases, only one carboxylic acid was used in the synthesis; no mixtures were used. See Holmes et al., Inorganic Chemistry, 24, 13, 1970 (1985); Chandrasekhar et al., Inorganica Chimica Acta, 522, 120378 (2021); and Xiao et al., Journal of Molecular Structure, 1190, 116 (2019).

[0016] However, Sn6 clusters have the problem of low solubility in common organic solvents. This becomes even more significant when alkyl groups with fewer carbon atoms are applied as substituents on tin. For example, the cluster (MeSn)6O6(O2CCH3)6 has been reported to have such low solubility that NMR spectra in solution could not be recorded. See Holmes et al., Inorganic Chemistry, Vol.27, No.16, 1988, 2887-2893. Consequently, Sn6 clusters with non-bulky alkyl groups as substituents on tin are rarely described in the literature. Despite the above, non-bulky substituents are considered advantageous for achieving higher packing density in the solid state. It has been shown that the solubility of Sn6 clusters containing less bulky substituents on tin can be increased in industrially acceptable solvents by applying mixed ligands. Using this approach, clusters containing small alkyl groups as well as formate and acetate ligands can be solubilized to a degree that they can be used for photoresist applications. This is demonstrated in Comparative Test 1.

[0017] The use of Sn6 clusters as EUV resists has been very limited. For example, Sharps et al. have mentioned the possibility of using Sn6 drum cluster systems as EUV resists. They tested the crystal density and intermolecular distance of non-functionalized drum cluster systems. The small alkyl group bonded to the Sn atom increases the cluster packing density by reducing the steric requirement per cluster. As a result, the intermolecular distance becomes smaller, which is considered advantageous for use as an EUV resist. See Sharps et al., Cryst.Res.Technol., 52, 1700081 (2017). The same group further investigated the use of Sn6-drum clusters (nBuSn)6O6(O2CCH3)6 for electron beam lithography applications. Dose curves are described there, and it is stated that this Sn6-cluster exhibits much lower sensitivity than comparable Sn12 clusters. See Sharps et al., Chem. Mater., 31, 4840-4850 (2019). However, in this publication, the (nBuSn)6O6(O2CCH3)6 material was coated with toluene, a solvent that cannot be used in industrial IC manufacturing processes due to its health and safety hazards.

[0018] According to the literature, the sensitivity of [(nBuSn)6O6(O2CCH3)6] compounds is inferior to that of Sn12 cluster materials in electron beam experiments. This was confirmed in internal experiments. Further interference lithography experiments using EUV radiation (13.5 nm) were performed using various Sn6 cluster materials. It was shown that the sensitivity of Sn6 materials can be dramatically increased by introducing appropriate ligand mixtures. This was demonstrated in comparative tests 2 and 3.

[0019] Despite the above, all synthesis relies on the use of a single alkyl-Sn starting material, not a mixture, and therefore there are no particular reports of Ra groups being mixed within a single cluster molecule.

[0020] It has been shown that the addition of acetic acid allows the preparation of Sn6 drum clusters [(nBuSn)6O6(O2CCH3)6] from larger Sn clusters. See, for example, Colton et al., J. Organomet. Chem., 476, 33 - 40 (1994) and Ribot et al., New J. Chem., 19, 1145 - 1153 (1995). However, only n-Bu derivatives have been used and only acetic acid has been used for the conversion. The addition of one equivalent of carboxylic acid per Sn atom results in the formation of pure Sn6 drum clusters.

[0021] Here, Sn6 drum clusters having mixed organic ligands and / or mixed carboxylate ligands are disclosed and claimed. Without being bound by theory, it is believed that introducing mixed organic ligands and / or mixed carboxylic acid ligands into the clusters can increase solubility in many organic solvents, particularly solvents relevant to industrial applications. The advantage of this is that the quality of the coating formed on a substrate by spin coating is improved. This improved coating can be observed in that the film thickness can be better adjusted, crystallization of the material is suppressed to obtain an amorphous film, and a smooth surface is generated. Another advantage of this is that there is a greater degree of tunability of the properties of the Sn clusters. SUMMARY OF THE INVENTION

[0022] In one embodiment, the disclosed and claimed subject matter is of the formula: [(R a1 Sn)(R a2 Sn)(R a3 Sn)(R a4 Sn)(R a5 Sn)(R a6 Sn)]O6[(O2C - R b1 )(O2C - R b2 )(O2C - R b3 )(O2C - R b4 )(O2C - R b5 )(O2C - R b6 )] [wherein, (A) Ra1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is an unsubstituted linear C1-C 10 Alkyl groups, halogen-substituted linear C1-C6 alkyl groups, amino-substituted linear C1-C6 alkyl groups, C5-C6 unsubstituted linear C1-C6 alkyl groups, unsubstituted branched C3-C 10 Branched C3-C cells substituted with alkyl groups and halogens. 10 Alkyl alkyl groups, C1-C 10 Heteroalkyl, amino group-substituted branched C3-C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH3)3, benzyl groups, C3-C8 unsubstituted cyclic alkyl groups, halogen-substituted C3-C8 cyclic alkyl groups, amino-substituted C3-C8 cyclic alkyl groups, C4-C8 unsubstituted aromatic groups, halogen-substituted C4-C8 aromatic groups, amino-substituted C4-C8 aromatic groups, C3-C 10 Heterocyclic groups, unsubstituted linear C2-C 10 Alkenyl group, unsubstituted branched C3-C 10 Alkenyl group, unsubstituted linear C2-C2 10 Alkynyl group and unsubstituted branched C4~C 10 Individually selected from the group consisting of alkynyl groups; (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of these is H; unsubstituted linear C1~C 10 Alkyl groups: Substituted linear C1-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl group; unsubstituted branched C3~C 10Alkyl groups: Substituted branched C3-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl groups; unsubstituted cyclic alkyl groups of C3-C8; linear C2-C 10 Alkenyl group; branched C3-C 10 Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, a linear C1-C4 chain, or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R rEach of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c (i) direct covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups, unsubstituted branched C3-C6 alkylene groups; and (C)(i)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 At least one of them is R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Unlike the rest of the and / or (ii)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 At least one of them is R b1 , R b2 , R b3 , R b4 , R b5 and R b6 This relates to Sn6-oxodrum clusters containing mixed organic ligands and / or mixed carboxylate ligands, which differ from the rest of the cluster.

[0023] In another embodiment, the subject matter disclosed and claimed is macroscopic formula: [(R a(i) Sn) 6-x (R a(ii) Sn) x ]O6[(O2C-R b(i) ) 6-y (O2C-R b(ii) ) y ] [In the formula, (A)(i)R a(i) ≠R a(ii) (ii)R a(i) and R a(ii) These are, respectively, unsubstituted linear C1-C 10An alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, a linear C1-C6 alkyl group substituted with a C5-C6 unsubstituted aromatic group, an unsubstituted branched C3-C 10 An alkyl group, a branched C3-C alkyl group substituted with a halogen 10 An alkyl group, a C1-C 10 A heteroalkyl group, a branched C3-C alkyl group substituted with an amino group 10 An alkyl group, an unsubstituted amine, a substituted amine, -Si(CH3)3, a benzyl group, an unsubstituted cyclic C3-C8 alkyl group, a C3-C8 cyclic alkyl group substituted with a halogen, a C3-C8 cyclic alkyl group substituted with an amino group, a C4-C8 unsubstituted aromatic group, a C4-C8 aromatic group substituted with a halogen, a C4-C8 aromatic group substituted with an amino group, a C3-C 10 A heterocyclic group, an unsubstituted linear C2-C 10 An alkenyl group, an unsubstituted branched C3-C 10 An alkenyl group, an unsubstituted linear C2-C 10 An alkynyl group and an unsubstituted branched C4-C 10 Individually selected from the group consisting of an alkynyl group; (B)(i)R b(i) ≠R b(ii) where (ii)R b(i) and R b(ii) are each, H; an unsubstituted linear C1-C 10 alkyl group; a -CN group, a -OH group, a -OR’ group, a -SR’ group or a -S-S-R’ group (wherein, R’ is a linear or branched C1-C4 alkyl group), a -C(=O)OR’’ group (wherein, R’’ is a linear or branched C1-C4 alkyl group), a -NO2 group, a halogen or a -C(=O)H group, a substituted linear C1-C 10 alkyl group; an unsubstituted branched C3-C 10 alkyl group; a -CN group, a -OH group, a -OR’ group, a -SR’ group or a -S-S-R’ group (wherein, R’ is a linear or branched C1-C4 alkyl group), a -C(=O)OR’’ group (wherein, R’’ is a linear or branched C1-C4 alkyl unit), a -NO2 group, a halogen or a -C(=O)H group, a substituted branched C3-C 10Alkyl groups; unsubstituted cyclic alkyl groups of C3-C8; linear C2-C 10 Alkenyl group; branched C3-C 10 Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups crelates to Sn6-oxo drum clusters containing a mixed organic ligand and / or a mixed carboxylate ligand that is (i) a direct covalent bond or (ii) an unsubstituted linear C1-C6 alkylene group or an unsubstituted branched C3-C6 alkylene group, and a mixture of compounds is also described.

[0024] In another aspect, the disclosed and claimed subject matter includes one or more mixtures of the above Sn6-oxo drum clusters. As will be understood by those skilled in the art, the average values of x and y may be different from the average values of the individual clusters that make up the mixture. Thus, in such mixtures, (i) x and y are each independently equal to an integer or fraction where 0 < x and / or y < 6, or (ii) one of x or y is 0 and the other of x or y is an integer or fraction where 0 < x and / or y < 6.

[0025] In another aspect, the disclosed and claimed subject matter includes using the disclosed and claimed Sn6-oxo clusters of the subject matter in a formulation useful in an EUV process or for preparing a formulation useful in an EUV process. Such formulations are used or can be used to pattern a radiation-sensitive coating in a process. The process includes (i) (a) prepared from the Sn6-oxo clusters described herein and / or using a process for its preparation, (b) having a uniform composition obtained by adjusting the water content of the solvent used to form the adjusted starting material solution within about ±15% of a target value, and (c) forming a coating on a substrate surface using a cluster solution having a selected water content of about 300 weight ppm to about 10,000 weight ppm, (ii) drying the coating, and (iii) irradiating the dried coating to form a latent image.

[0026] In another aspect, the disclosed and claimed subject matter includes a method for preparing the Sn6-oxo clusters described herein.

[0027] The summary section of this invention does not specify all embodiments and / or progressively novel aspects of the disclosed and claimed subject matter. Instead, the summary of this invention only provides a preliminary discussion of different embodiments and the corresponding points of novelty over the prior art and known techniques. For further details and / or possible aspects of the disclosed and claimed subject matter and embodiments, the reader is referred to the section on forms for carrying out the invention and the corresponding figures of this disclosure, as further discussed below.

[0028] The discussion of the order of the different steps described herein is presented for clarity. Generally, the steps disclosed herein can be executed in any suitable order. In addition, each of the different features, techniques, configurations, etc. disclosed herein may be discussed at different places in this disclosure, but it is intended that each concept can be executed independently of each other or in combination with each other as appropriate. Therefore, the disclosed and claimed subject matter can be embodied in many different forms.

[0029]

Brief Description of the Drawings

[0030] The accompanying drawings are included to provide a further understanding of the disclosed subject matter, are incorporated herein, form a part of this specification, show embodiments of the disclosed subject matter, and together with the detailed description, serve to explain the principles of the disclosed subject matter. The drawings are as follows.

[0031] [Figure 1] Shows the 119Sn NMR of the Sn6 cluster of Example 1.

[0032] [Figure 2] Shows the 119Sn NMR of the Sn6 cluster of Example 2.

[0033] [Figure 3] Shows the 119Sn NMR of the Sn6 cluster of Example 3.

[0034] [Figure 4] Shows the 119Sn NMR of the Sn6 cluster of Example 4.

[0035] [Figure 5] Shows the 119Sn NMR of the solution sample versus the redissolved material of the Sn6 cluster of Example 5.

[0036] [Figure 6] Shows the line space pattern of [(nBuSn)6O6(O2CCH3)6] with an 80 nm pitch.

[0037] [Figure 7] Shows the line space pattern of [(nBuSn)6O6(O2CH)6] with an 80 nm pitch.

[0038] [Figure 8] Shows the line space pattern of [(MeSn)6O6(O2CH)3(O2CC4H5O2)3] with a 70 nm pitch.

[0039] [Figure 9] Shows the line space pattern of [(MeSn)6O6(O2CH)3(O2C(CHS2C3H6))3] with an 80 nm pitch.

[0040] [Figure 10] Shows the 119Sn-119Sn-INADEQUATE NMR spectrum of the Sn6 cluster of Example 9.

[0041] [Figure 11] Shows the mass spectrum of the Sn6 cluster of Example 9.

[0042] [Figure 12] Shows the mass spectrum of the Sn6 cluster of Example 11.

[0043] [Figure 13]The mass spectrum of the Sn6 cluster from Example 16 is shown.

[0044] [Figure 14] The crystal structure of (nBuSn)6O6(O2CCH3)6 is shown.

[0045] definition

[0046] Unless otherwise specified, the following terms used in this specification and in the claims have the following meanings in this application:

[0047] In this application, the use of the singular form includes the plural form, and the words “a,” “an,” and “the” mean “at least one” unless otherwise specified. Furthermore, the use of the term “including,” as well as other forms such as “includes” and “included,” is not limited. Also, terms such as “element” or “component” include both elements or components containing one unit and elements or components containing two or more units, unless otherwise specified. Where used herein, unless otherwise indicated, the conjunction “and” is intended to be inclusive, and the conjunction “or” is not intended to be exclusive. For example, the phrase “or alternatively” is intended to be exclusive. Where used herein, the terms “and / or” refer to any combination of the aforementioned elements, including the use of a single element.

[0048] As used herein, "approximately" or "about" is intended to correspond to a value within ±5% of the stated value.

[0049] The term "C" used herein x~y (x and y are integers, also called "whole number")) indicates the number of carbon atoms in the chain. For example, C 1~6Alkyl refers to an alkyl chain having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl). Unless otherwise specified, the chain may be linear or branched. The term "chain" refers to a linear or branched hydrocarbon group, preferably alkyl, alkenyl, and alkynyl, unless otherwise specified.

[0050] Unless otherwise specified, “alkyl” refers to a hydrocarbon group that may be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). Preferred acyclic groups may be methyl, ethyl, n- or iso-propyl, n-, iso, or tert-butyl, linear or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise specified, alkyl refers to a portion of 1 to 10 carbon atoms. Cyclic alkyl groups may be monocyclic or polycyclic. Preferred examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl groups. As described herein, cyclic alkyl groups may have any acyclic alkyl group as a substituent. These alkyl portions may be substituted or unsubstituted.

[0051] "Alkyl halide" refers to a linear, cyclic, or branched saturated alkyl group as defined above, in which one or more hydrogen atoms are replaced with halogens (e.g., F, Cl, Br, and I). Therefore, for example, fluorinated alkyl groups (also known as "fluoroalkyls") refer to a linear, cyclic, or branched saturated alkyl group as defined above, in which one or more hydrogen atoms are replaced with fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.). Such haloalkyl moieties (e.g., fluoroalkyl moieties) may be unsubstituted or further substituted if they are not perhalogenated (total halogenated) / polyhalogenated.

[0052] "Alkoxy" (also known as "alkyloxy") refers to the alkyl group defined above, which is bonded via an oxy (-O-) moiety (for example, methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.). These alkoxy moieties may or may not be substituted.

[0053] "Alkylcarbonyl" refers to the alkyl group defined above, which is bonded via a carbonyl group (-C(=O-)) moiety (for example, methylcarbonyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, cyclopentylcarbonyl, etc.). These alkylcarbonyl moieties may or may not be substituted.

[0054] "Halo" or "halide" refers to halogens (for example, F, Cl, Br, and I).

[0055] "Hydroxy" (also known as "hydroxyl") refers to the -OH group.

[0056] The term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Examples of aryl groups include, but are not limited to, phenyl, 1-phenylethyl (Ph(Me)CH-), 1-phenyl-1-methyl-ethyl (Ph(Me)2C-), benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0057] The alkoxy ligand Ot-amyl represents O-CCH3CH3CH2CH3.

[0058] In addition to known representations of covalent bond points, [ka] This notation is also intended to indicate the covalent bond point.

[0059] Unless otherwise specified, "alkylene" means a straight-chain saturated divalent hydrocarbon group of one or more carbon atoms, or a branched saturated divalent hydrocarbon group of 3 to 6 carbon atoms (e.g., methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, etc.) in the disclosed and claimed compound. 1 and R 2 The bond between the alkylene and the ethylene group functions as an ethylene bridge, for example. Specific examples of alkylene bonds include methylene (-CH2-), ethylene (-CH2CH2-), substituted ethylene (e.g., -CH(CH3)CH2-); -CH(CH3)CH(CH3)-; -C(CH3)2CH2-), propylene (-CH2CH2CH2-), and substituted propylene.

[0060] "Heteroalkylene" refers to the -(alkylene)- radicals defined above, in which one, two, or three carbon atoms in the alkylene chain are replaced with -O-, N(H, alkyl, or substituted alkyl), S, SO, SO2, or CO. In some preferred embodiments, the carbon atoms are replaced with O or N.

[0061] "Heteroalkyl" refers to an alkyl group as defined above in which one, two, or three carbon atoms in the alkyl chain are replaced with -O-, N(H, alkyl, or substituted alkyl), S, SO, SO2, or CO. In some preferred embodiments, the carbon atoms are replaced with O or N.

[0062] Unless otherwise specified, the term "substituted" when referring to alkyl, alkoxy, fluorinated alkyl, etc., refers to those parts of these that have one or more substituents, including but not limited to alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxy, amino, and aminoalkyl. Similarly, the term "unsubstituted" refers to these same parts that do not have substituents other than hydrogen.

[0063] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described herein. All documents or parts of documents cited herein, including but not limited to patents, patent applications, articles, books, and professional works, are expressly incorporated herein by reference in whole for any purpose. If any incorporated document or similar material defines a term in a manner that conflicts with the definitions of terms in this application, this application shall prevail. [Modes for carrying out the invention]

[0064] It should be understood that both the general description above and the detailed description below are illustrative and descriptive, and do not limit the subject matter claimed. The purpose, features, advantages, and ideas of the disclosed subject matter will be apparent to those skilled in the art from the descriptions provided herein, and the disclosed subject matter is readily implementable by those skilled in the art based on the descriptions present herein. Any descriptions of “preferred embodiments” and / or examples illustrating a preferred way of carrying out the disclosed subject matter are included for descriptive purposes and are not intended to limit the scope of the claims.

[0065] Sn6 oxoclusters and their mixtures

[0066] In one embodiment, the subject matter disclosed and claimed is formula: [(R a1 Sn)(R a2 Sn)(R a3 Sn)(R a4 Sn)(R a5 Sn)(R a6 Sn)]O6[(O2C-R b1 )(O2C-R b2 )(O2C-R b3 )(O2C-R b4 )(O2C-R b5 )(O2C-R b6 )] [In the formula, (A)R a1 , R a2 , R a3, R a4 , R a5 and R a6 Each of these is an unsubstituted linear C1-C 10 Alkyl groups, halogen-substituted linear C1-C6 alkyl groups, amino-substituted linear C1-C6 alkyl groups, C5-C6 unsubstituted linear C1-C6 alkyl groups, unsubstituted branched C3-C 10 Branched C3-C cells substituted with alkyl groups and halogens. 10 Alkyl alkyl groups, C1-C 10 Heteroalkyl groups, branched C3-C groups substituted with amino groups 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH3)3, benzyl groups, C3-C8 unsubstituted cyclic alkyl groups, halogen-substituted C3-C8 cyclic alkyl groups, amino-substituted C3-C8 cyclic alkyl groups, C4-C8 unsubstituted aromatic groups, halogen-substituted C4-C8 aromatic groups, amino-substituted C4-C8 aromatic groups, C3-C 10 Heterocyclic groups, unsubstituted linear C2-C 10 Alkenyl group, unsubstituted branched C3-C 10 Alkenyl group, unsubstituted linear C2-C2 10 Alkynyl group and unsubstituted branched C4~C 10 Individually selected from the group consisting of alkynyl groups; (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of these is H; unsubstituted linear C1~C 10 Alkyl groups: Substituted linear C1-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl group; unsubstituted branched C3~C 10Alkyl groups: Substituted branched C3-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl groups; unsubstituted cyclic alkyl groups of C3-C8; linear C2-C 10 Alkenyl group; branched C3-C 10 Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, a linear C1-C4 chain, or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R rEach of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c (i) direct covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups, unsubstituted branched C3-C6 alkylene groups; and (C)(i)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 At least one of them is R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Unlike the rest of the and / or (ii)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 At least one of them is R b1 , R b2 , R b3 , R b4 , R b5 and R b6 This relates to Sn6-oxodrum clusters containing mixed organic ligands and / or mixed carboxylate ligands, which differ from the rest of the cluster.

[0067] As those skilled in the art will understand, the Sn6-oxo drum cluster of the disclosed and claimed subject matter has the following general structure: [ka]

[0068] In one embodiment of this configuration, R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of them is the same. In one embodiment of this design, R a1 , R a2, R a3 , R a4 , R a5 and R a6 At least one of them is R a1 , R a2 , R a3 , R a4 , R a5 and R a6 It differs from the others. In one embodiment of this design, R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is the same. In one embodiment of this design, R b1 , R b2 , R b3 , R b4 , R b5 and R b6 At least one of them is R b1 , R b2 , R b3 , R b4 , R b5 and R b6 It differs from the others. In one embodiment of this design, R a1 , R a2 , R a3 , R a4 , R a5 , and R a6 At least one of them is R a1 , R a2 , R a3 , R a4 , R a5 , and R a6 Unlike the others, R b1 , R b2 , R b3 , R b4 , R b5 , and R b6 At least one of them is R b1 , R b2 , R b3 , R b4 , R b5 , and R b6 It is different from the others.

[0069] In a further embodiment of this embodiment (A)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is individually selected from the group consisting of unsubstituted linear C1-C4 alkyl groups, unsubstituted branched C3-C4 alkyl groups, unsubstituted linear C2-C6 alkenyl groups, unsubstituted branched C3-C6 alkenyl groups, and C4-C6 unsubstituted aromatic groups.

[0070] In a further embodiment of this embodiment (A)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, -CH2CH2CH2CH3, -C6H5, and -CH2-C6H5.

[0071] In a further embodiment of this embodiment (A)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, and -CH2CH2CH2CH3.

[0072] In a further embodiment of this embodiment (A)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, and -CH2CH2CH2CH3.

[0073] In a further embodiment of this design, (A)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -CH=CH2, and -CH2CH2CH2CH3.

[0074] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen or -C(=O)H group; unsubstituted branched C3-C6 alkyl group; -CN group, -OH group Substituted branched C3-C6 alkyl groups substituted with one or more of the following: -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group; unsubstituted cyclic alkyl groups of C3-C6; linear C2-C6 alkenyl groups; branched C3-C6 alkenyl groups, 5-membered heterocycles, and 6-membered heterocycles; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0075] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, or -C(=O)H group; unsubstituted branched C3-C 6 alkyl groups; substituted branched C3-C6 alkyl groups substituted with one or more of the following: -CN group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, or -C(=O)H group; linear C2-C6 alkenyl groups; branched C3-C6 alkenyl groups, [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0076] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; substituted linear C1-C6 alkyl group substituted with one or more of the following: -CN group, -OR' group (wherein R' is a linear or branched C1-C4 alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group); unsubstituted branched C3-C6 alkyl group; substituted branched C3-C6 alkyl group substituted with one or more of the following: -CN group, -OR' group (wherein R' is a linear or branched C1-C4 alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit); [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0077] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group; or -OR' group (wherein R' is a linear or branched C1-C4 alkyl group); an unsubstituted branched C3-C6 alkyl group substituted with one or more of the following: -CN group; or -OR' group (wherein R' is a linear or branched C1-C4 alkyl group); [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0078] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0079] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0080] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0081] In a further embodiment of this design, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0082] In a further embodiment of this design, (A)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -CH=CH2, and -CH2CH2CH2CH3, (B)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0083] In another embodiment, the subject matter disclosed and claimed comprises one or more mixtures of the above-mentioned Sn6-oxodrum clusters.

[0084] Exemplary Sn6-oxocluster compounds

[0085] In one embodiment described above, the disclosed Sn6-oxo drum cluster is (i)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 A part of it (for example, half) is the same first base ("R a(i) ) and R a1 , R a2 , R a3 , R a4 , R a5 and R a6 The remainder is the first base ("R a(i) ) is the same second base ("R" a(ii) ) and / or (ii)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 A part of it (for example, half) is the same first base ("R b(i) ) and R b1 , R b2 , R b3 , R b4 , R b5 and R b6 The remainder is the first base ("R b(i) ) is the same second base ("R" b(ii) This includes being ").Therefore, the disclosed and claimed Sn6-oxo drum cluster is of formula: [(R a(i) Sn) 6-x (R a(ii) Sn) x ]O6[(O2C-R b(i) ) 6-y (O2C-R b(ii) ) y ] [In the formula, (A)(i)R a(i) ≠R a(ii) (ii)R a(i) and R a(ii) These are, respectively, unsubstituted linear C1-C 10Alkyl groups, halogen-substituted linear C1-C6 alkyl groups, amino-substituted linear C1-C6 alkyl groups, C5-C6 unsubstituted linear C1-C6 alkyl groups, unsubstituted branched C3-C 10 Branched C3-C cells substituted with alkyl groups and halogens. 10 Alkyl alkyl groups, C1-C 10 Heteroalkyl groups, branched C3-C groups substituted with amino groups 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH3)3, benzyl groups, C3-C8 unsubstituted cyclic alkyl groups, halogen-substituted C3-C8 cyclic alkyl groups, amino-substituted C3-C8 cyclic alkyl groups, C4-C8 unsubstituted aromatic groups, halogen-substituted C4-C8 aromatic groups, amino-substituted C4-C8 aromatic groups, C3-C 10 Heterocyclic groups, unsubstituted linear C2-C 10 Alkenyl group, unsubstituted branched C3-C 10 Alkenyl group, unsubstituted linear C2-C2 10 Alkynyl group and unsubstituted branched C4~C 10 Individually selected from the group consisting of alkynyl groups; (B)(i)R b(i) ≠R b(ii) (ii)R b(i) and R b(ii) These are H; unsubstituted linear C1~C respectively. 10 Alkyl groups: Substituted linear C1-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl group; unsubstituted branched C3~C 10 Alkyl groups: Substituted branched C3-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group. 10Alkyl groups; unsubstituted cyclic alkyl groups of C3-C8; linear C2-C 10 Alkenyl group; branched C3-C 10 Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c (i) direct covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups, unsubstituted branched C3-C6 alkylene groups; and (C)(i) x and y are each independently equal to an integer between 1 and 5, or (ii) one of x or y is 0 and the other of x or y is an integer between 1 and 5, comprising a mixed organic ligand and / or a mixed carboxylate ligand.

[0086] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of unsubstituted linear C1-C4 alkyl groups, unsubstituted branched C3-C4 alkyl groups, unsubstituted linear C2-C6 alkenyl groups, unsubstituted branched C3-C6 alkenyl groups, and C4-C6 unsubstituted aromatic groups.

[0087] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, -CH2CH2CH2CH3, -C6H5, and -CH2-C6H5.

[0088] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, and -CH2CH2CH2CH3.

[0089] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, and -CH2CH2CH2CH3.

[0090] In a further embodiment of this design, (A)R a(i) and R a(ii)Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -CH=CH2, and -CH2CH2CH2CH3.

[0091] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen or -C(=O)H group; unsubstituted branched C3-C6 alkyl group; -CN group, -OH group Substituted branched C3-C6 alkyl groups substituted with one or more of the following: -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group; unsubstituted cyclic alkyl groups of C3-C6; linear C2-C6 alkenyl groups; branched C3-C6 alkenyl groups, 5-membered heterocycles, and 6-membered heterocycles; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0092] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, or -C(=O)H group; unsubstituted branched C3-C 6 alkyl groups; substituted branched C3-C6 alkyl groups substituted with one or more of the following: -CN group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, or -C(=O)H group; linear C2-C6 alkenyl groups; branched C3-C6 alkenyl groups, [ka] In the formula, (i) n = 1 to 5, and (ii) each Rr These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0093] In a further embodiment of this design, (B)R b(i) and R b(ii)Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; substituted linear C1-C6 alkyl group substituted with one or more of the following: -CN group, -OR' group (wherein R' is a linear or branched C1-C4 alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group); unsubstituted branched C3-C6 alkyl group; substituted branched C3-C6 alkyl group substituted with one or more of the following: -CN group, -OR' group (wherein R' is a linear or branched C1-C4 alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit); [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R rEach of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0094] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group; or -OR' group (wherein R' is a linear or branched C1-C4 alkyl group); an unsubstituted branched C3-C6 alkyl group substituted with one or more of the following: -CN group; or -OR' group (wherein R' is a linear or branched C1-C4 alkyl group); [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R rEach of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0095] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0096] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0097] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0098] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0099] In a further embodiment of this design, (A)R a(i) and R a(ii)Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -CH=CH2, and -CH2CH2CH2CH3, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0100] In one embodiment of this invention, the subject matter disclosed and claimed is (i)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 A part of it (for example, half) is the same first base ("R a(i) ) and R a1 , R a2 , R a3 , R a4 , R a5 and R a6 The remainder is the first base ("R a(i) ) is the same second base ("R" a(ii) 」) and (ii)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 Each of them is the same base (i.e., R b1 =R b2 =R b3 =R b4 =R b5 =R b6 ; "R b It contains an Sn6-oxo drum cluster, which is ''. As those skilled in the art will understand, a(i) and R a(ii) The ratio of R a(i) :R a(ii) = (5-u):(1+u) [where u is an integer from 0 to 4] can be defined as the ratio. Therefore, this type of mixed ligand cluster can be defined by the formula: [(R a(i) Sn) 6-x (R a(ii) Sn) x]O6(O2C-R b ) has 6 [where x = an integer from 1 to 5].

[0101] In another embodiment of this design, the subject matter disclosed and claimed is (i)R a1 , R a2 , R a3 , R a4 , R a5 and R a6 Each of them is the same base (i.e., R a1 =R a2 =R a3 =R a4 =R a5 =R a6 ; "R a 」) and (ii)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 A part of it (for example, half) is the same first base ("R b(i) ) and R b1 , R b2 , R b3 , R b4 , R b5 and R b6 The remainder is the first base ("R b(i) ) is the same second base ("R" b(ii) It contains an Sn6-oxo drum cluster, which is ''. As those skilled in the art will understand, b(i) and R b(ii) The ratio of R b(i) :R b(ii) = (5-p):(1+p) [where p is an integer from 0 to 4] can be defined as the ratio. Therefore, this type of mixed ligand cluster can be defined by the equation: (R a Sn)6O6[(O2C-R b(i) ) 6-y (O2C-R b(ii) ) y [The formula has y = integers from 1 to 5.]

[0102] In a further embodiment of this design, the subject matter disclosed and claimed is (i)R a1 , R a2, R a3 , R a4 , R a5 and R a6 A part of it (for example, half) is the same first base ("R a(i) ) and R a1 , R a2 , R a3 , R a4 , R a5 and R a6 The remainder is the first base ("R a(i) ) is the same second base ("R" a(ii) 」) and (ii)R b1 , R b2 , R b3 , R b4 , R b5 and R b6 A part of it (for example, half) is the same first base ("R b(i) ) and R b1 , R b2 , R b3 , R b4 , R b5 and R b6 The remainder is the first base ("R b(i) ) is the same second base ("R" b(ii) It contains an Sn6-oxo drum cluster, which is ''. As those skilled in the art will understand, a(i) and R a(ii) The ratio of R a(i) :R a(ii) = (5-u):(1+u) [where u is an integer from 0 to 4] can be defined as the ratio of R b(i) and R b(ii) The ratio of R b(i) :R b(ii) =(5-p):(1+p)[where p=an integer from 0 to 4] can be defined as the ratio. Therefore, this type of mixed ligand cluster can be defined by the formula:[(R a(i) Sn) 6-x (R a(ii) Sn) x ]O6[(O2C-R b(i) ) 6-y (O2C-R b(ii) ) y [In the formula, x and y are each independent integers between 1 and 5.]

[0103] As those skilled in the art will understand, in mixtures of different Sn6-oxodrum clusters, x and / or y can be fractional (see below), and the ratio of each is R a(i) :R a(ii) and / or R b(i) :R b(ii) It can be expressed as a non-integer / fraction (for example, R a(i) :R a(ii) (For example, when x = 4.5, the ratio can be 1.5:4.5). On the other hand, when x and / or y are integers, the ratio of each is R a(i) :R a(ii) and / or R b(i) :R b(ii) It can also be represented as an integer (for example, R b(i) :R b(ii) (For example, when y=3, the ratio can be 3:3). Examples of integer ratios of Sn6-oxodrum clusters included in the disclosed and claimed subject matter are shown in Table 1 below. [Table 1-1] [Table 1-2] [Table 1-3]

[0104] As those skilled in the art will understand, a1 , R a2 , R a3 , R a4 , R a5 and R a6 The proportion, and / or R b1 , R b2 , R b3 , R b4 , R b5 and R b6 The proportions of each can be stoichiometrically controlled during the synthesis of the Sn6-oxocluster. Furthermore, the subject matter disclosed and claimed includes mixtures and formulations containing the above compounds, particularly those specified in Table 1.

[0105] Sn6-oxo cluster mixture

[0106] In another aspect, the disclosed and claimed subject matter includes one or more mixtures of the above Sn6-oxo drum clusters. As will be understood by those skilled in the art, the average values of x and y may be different from the average values of the individual clusters that make up the mixture. Thus, in such mixtures, (i) x and y are each independently equal to an integer or fraction where 0 < x and / or y < 6, or (ii) one of x or y is 0 and the other of x or y is an integer or fraction where 0 < x and / or y < 6. Thus, the disclosed and claimed subject matter includes a mixture of the above Sn6-oxo drum clusters, and the mixture of Sn6-oxo drum clusters has the formula: [(R a(i) Sn) 6-x (R a(ii) Sn) x O6[(O2C-R b(i) ) 6-y (O2C-R b(ii) ) y [wherein (A)(i) R a(i) ≠R a(ii) and (ii) R a(i) and R a(ii) are each, an unsubstituted straight-chain C1-C 10 alkyl group, a straight-chain C1-C6 alkyl group substituted with a halogen, a straight-chain C1-C6 alkyl group substituted with an amino group, a straight-chain C1-C6 alkyl group substituted with a C5-C6 unsubstituted aromatic group, an unsubstituted branched C3-C 10 alkyl group, a branched C3-C 10 alkyl group substituted with a halogen, a C1-C 10 heteroalkyl group, a branched C3-C 10 alkyl group substituted with an amino group, an unsubstituted amine, a substituted amine, -Si(CH3)3, a benzyl group, an unsubstituted C3-C8 cyclic alkyl group, a C3-C8 cyclic alkyl group substituted with a halogen, a C3-C8 cyclic alkyl group substituted with an amino group, a C4-C8 unsubstituted aromatic group, a C4-C8 aromatic group substituted with a halogen, a C4-C8 aromatic group substituted with an amino group, a C3-C​10 Heterocyclic groups, unsubstituted linear C2-C 10 Alkenyl group, unsubstituted branched C3-C 10 Alkenyl group, unsubstituted linear C2-C2 10 Alkynyl group and unsubstituted branched C4~C 10 Individually selected from the group consisting of alkynyl groups; (B)(i)R b(i) ≠R b(ii) (ii)R b(i) and R b(ii) These are H; unsubstituted linear C1~C respectively. 10 Alkyl groups: Substituted linear C1-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl group; unsubstituted branched C3~C 10 Alkyl groups: Substituted branched C3-C4 alkyl groups substituted with one or more of the following: -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group. 10 Alkyl groups; unsubstituted cyclic alkyl groups of C3-C8; linear C2-C 10 Alkenyl group; branched C3-C 10 Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Group (where n = 1 to 4);

Chem.

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Chem.

[0107] In a further aspect of this embodiment, (A) each of R a(i) and R a(ii) is individually selected from the group consisting of an unsubstituted straight-chain C1 - C4 alkyl group, an unsubstituted branched C3 - C4 alkyl group, an unsubstituted straight-chain C2 - C6 alkenyl group, an unsubstituted branched C3 - C6 alkenyl group, and a C4 - C6 unsubstituted aromatic group).

[0108] In a further aspect of this embodiment, (A) R a(i) and R a(ii)Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, -CH2CH2CH2CH3, -C6H5, and -CH2-C6H5.

[0109] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -CH2CH2CH=CH2, and -CH2CH2CH2CH3.

[0110] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -C(CH3)3, -CH=CH2, -CH2CH=CH2, and -CH2CH2CH2CH3.

[0111] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -CH=CH2, and -CH2CH2CH2CH3.

[0112] In a further embodiment of this design, (B)R b(i) and R b(ii)Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group, -OH group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, halogen or -C(=O)H group; unsubstituted branched C3-C6 alkyl group; -CN group, -OH group Substituted branched C3-C6 alkyl groups substituted with one or more of the following: -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, halogen, or -C(=O)H group; unsubstituted cyclic alkyl groups of C3-C6; linear C2-C6 alkenyl groups; branched C3-C6 alkenyl groups, 5-membered heterocycles, and 6-membered heterocycles; [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n=1 to 4 in the formula), [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each Rm The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0113] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group), -NO2 group, or -C(=O)H group; unsubstituted branched C3-C 6 alkyl groups; substituted branched C3-C6 alkyl groups substituted with one or more of the following: -CN group, -OR' group, -SR' group or -SS-R' group (wherein R' is a linear or branched C1-C4 alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit), -NO2 group, or -C(=O)H group; linear C2-C6 alkenyl groups; branched C3-C6 alkenyl groups, [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0114] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; substituted linear C1-C6 alkyl group substituted with one or more of the following: -CN group, -OR' group (wherein R' is a linear or branched C1-C4 alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl group); unsubstituted branched C3-C6 alkyl group; substituted branched C3-C6 alkyl group substituted with one or more of the following: -CN group, -OR' group (wherein R' is a linear or branched C1-C4 alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C1-C4 alkyl unit); [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 4); [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0115] In a further embodiment of this design, (B)R b(i) and R b(ii)Each of these is a substituted linear C1-C6 alkyl group substituted with one or more of the following: -H; unsubstituted linear C1-C6 alkyl group; -CN group; or -OR' group (wherein R' is a linear or branched C1-C4 alkyl group); an unsubstituted branched C3-C6 alkyl group substituted with one or more of the following: -CN group; or -OR' group (wherein R' is a linear or branched C1-C4 alkyl group); [ka] In the formula, (i) n = 1 to 5, and (ii) each R r These are, individually, unsubstituted methylene groups or methylene groups substituted with one or two C1-C4 alkyl groups. [ka] Base (where n = 1 to 6 in the formula); [ka] Base (wherein each X is individually selected from O and S, and n=1 to 4); [ka] group (wherein each R m The group is independently selected from H, or from a linear C1-C4 chain or a branched C3-C4 chain. [ka] In the formula, (i) n = 3 to 5, and (ii) each R r Each of the above groups is individually selected from the group consisting of: an unsubstituted methylene group or a methylene group substituted with one or two C1-C4 alkyl groups, and R in each of the above groups c These are (i) directly covalent bonds, or (ii) unsubstituted linear C1-C6 alkylene groups and unsubstituted branched C3-C6 alkylene groups.

[0116] In a further embodiment of this design, (B)R b(i) and R b(ii)Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0117] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0118] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0119] In a further embodiment of this design, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0120] In a further embodiment of this design, (A)R a(i) and R a(ii) Each of these is individually selected from the group consisting of -CH3, -CH(CH3)2, -CH=CH2, and -CH2CH2CH2CH3, (B)R b(i) and R b(ii) Each of them is -H, [ka] They are individually selected from the group consisting of the following.

[0121] Preparation process for Sn6 oxoclusters

[0122] As described above, the disclosed subject matter further includes a process for synthesizing the disclosed and claimed Sn6-oxocluster.

[0123] In another embodiment, the subject matter disclosed and claimed is a mixed organic ligand (i.e., R a This invention relates to a process for preparing Sn6-oxodrum clusters having ligands. A mixture of at least two monoorgano-Sn starting materials, each having a different organic group bonded to a Sn atom and a ligand X that is typically alkoxy, is optionally prepared in an organic solvent or solvent mixture. Water (as pure water or as a solution in an organic solvent or solvent mixture) is added while stirring. While continuing to stir, a carboxylic acid (1 equivalent relative to total Sn) is added to the reaction solution, either as a pure substance or as a solution in an organic solvent or solvent mixture. The reaction solution is typically stirred for several hours or overnight. The Sn6-oxodrum clusters can be isolated by optionally removing the solvent under reduced pressure and / or high temperature by filtration or evaporation. [ka]

[0124] In one embodiment, the solvent is selected from toluene, THF, PGME, cyclohexanone, 2-heptanone, CPME, anisole, and mixtures thereof. In one embodiment, each addition step is carried out at room temperature, but alternatively, it can be carried out at low or high temperatures in the range between the freezing point and boiling point of the solvent. For example, the addition of water may be carried out at room temperature, the addition of a carboxylic acid may be carried out at a high temperature, and vice versa. The addition steps may also be carried out at the same temperature. Thus, in one embodiment, some or all of the steps of the process are carried out at temperatures ranging from about 0°C to below the boiling point of the solvent used. In another embodiment, some or all of the steps of the process are carried out at temperatures ranging from about 10°C to about 60°C. In another embodiment, some or all of the steps of the process are carried out at temperatures ranging from about 15°C to about 30°C. In another embodiment, some or all of the steps of the process are carried out at temperatures ranging from about 18°C ​​to approximately room temperature. In another embodiment, all steps are carried out at temperatures ranging from approximately room temperature to below the boiling point of the solvent used. In another embodiment, all of the steps of the process are carried out at room temperature.

[0125] In one embodiment, the yield of Sn6-oxo clusters by this process is approximately 80% or higher. In another embodiment, the yield of Sn6-oxo clusters by this process is approximately 85% or higher. In yet another embodiment, the yield of Sn6-oxo clusters by this process is approximately 90% or higher. In yet another embodiment, the yield of Sn6-oxo clusters by this process is approximately 95% or higher.

[0126] In another embodiment, the subject matter disclosed and claimed is a mixed carboxylate ligand (i.e., R b This relates to a process for preparing Sn6-oxodrum clusters having ligands. In a typical synthesis, monoorgano (i.e., all R) aThe Sn starting material (which is the same as Sn) and ligand X (usually an alkoxy) are optionally reacted with water in an organic solvent or a mixture of solvents (e.g., THF). Stirring is continued, and a mixture of acids (total amount of carboxylate = 1 equivalent relative to Sn) is added to the reaction solution, either as a pure substance or as a solution in the organic solvent or solvent mixture. Stirring is further continued, typically for several hours or overnight. The Sn6-oxocluster can be isolated by optionally removing the solvent under reduced pressure and / or high temperature by filtration or evaporation. [ka]

[0127] In one embodiment, the solvent is selected from toluene, THF, PGME, cyclohexanone, 2-heptanone, CPME, anisole, and mixtures thereof. In one embodiment, each addition step is carried out at room temperature, but alternatively, it can be carried out at low or high temperatures in the range between the freezing point and boiling point of the solvent. For example, the addition of water may be carried out at room temperature, and the addition of a carboxylic acid may be carried out at a high temperature, or vice versa. The addition steps may also be carried out at the same temperature.

[0128] In one embodiment, the yield of Sn6-oxo clusters by this process is approximately 80% or higher. In another embodiment, the yield of Sn6-oxo clusters by this process is approximately 85% or higher. In yet another embodiment, the yield of Sn6-oxo clusters by this process is approximately 90% or higher. In yet another embodiment, the yield of Sn6-oxo clusters by this process is approximately 95% or higher.

[0129] In one embodiment, the subject matter disclosed and claimed is a mixed carboxylate ligand (i.e., R bThis invention relates to a process for preparing Sn6-oxodrum clusters having ligands. Two (or more) "pure" Sn6-oxodrum clusters having different carboxylate ligands are mixed in solution to obtain Sn6-oxodrum clusters having mixed carboxylate ligands. The process is schematically shown for mixing two different cluster materials. [ka]

[0130] In another embodiment, this process involves a mixed organic ligand (i.e., R a Ligand) and mixed carboxylate ligand (i.e., R b This invention relates to a method for preparing Sn6-oxodrum clusters having ligands. A mixture of at least two monoorgano-Sn starting materials, each having a different organic group bonded to a Sn atom and a ligand X that is typically alkoxy, is optionally prepared in an organic solvent. Water (as pure water or as a solution in an organic solvent or a mixture of organic solvents) is added while stirring. A mixture of acids (total amount of carboxylate = 1 equivalent relative to Sn) is added to the reaction solution either as a pure substance or as a solution in an organic solvent or a mixture of solvents. Stirring is further continued, typically for several hours or overnight. The Sn6-oxodrum clusters can be isolated by optionally removing the solvent under reduced pressure and / or high temperature by filtration or evaporation. [ka]

[0131] In one embodiment, the solvent is selected from toluene, THF, PGME, cyclohexanone, 2-heptanone, CPME, anisole, and mixtures thereof. In one embodiment, each addition step is carried out at room temperature, but alternatively, it can be carried out at low or high temperatures in the range between the freezing point and boiling point of the solvent. For example, the addition of water may be carried out at room temperature, and the addition of a carboxylic acid may be carried out at a high temperature, or vice versa. The addition steps may also be carried out at the same temperature.

[0132] In one embodiment, the yield of Sn6-oxo clusters by this process is approximately 80% or higher. In another embodiment, the yield of Sn6-oxo clusters by this process is approximately 85% or higher. In yet another embodiment, the yield of Sn6-oxo clusters by this process is approximately 90% or higher. In yet another embodiment, the yield of Sn6-oxo clusters by this process is approximately 95% or higher.

[0133] Monitoring of mixed cluster formation: Sn6 drum clusters without mixed ligands are known in the literature, R a =Me, nBu, and iPr have been shown to produce sharp NMR signals in the range of approximately -440 ppm to -520 ppm. See Example 3, Figure 6. The exact chemical shift of each signal depends on the coordination environment, and therefore depends on the coordination number, carboxylate ligand, and alkyl substituent (R a The result is a function of ). When a mixed cluster species is formed, these signals broaden because there are multiple Sn atoms with slightly altered chemical environments within the cluster. This broadening indicates a mixed cluster, and a representative spectrum is shown in the experimental example. Different R in the cluster a If Sn atoms with groups (such as Me and nBu) are present, a signal spreading across each type of Sn atom may occur.

[0134] Generally, cluster formation occurs when the concentration of the material is sufficiently high. 119 It can be directly monitored in solution via Sn-NMR. Higher concentrations can be achieved by partial removal of the solvent. For these experiments, capillary inserts containing a deuterated solvent are typically used. In this way, the reaction solution does not change with the addition of further solvent. Another approach is to completely remove the solvent and then redissolve the compound in a deuterated solvent to isolate it. In Example 5 (see Figure 12), the mixed compound in the reaction solution and the redissolved solid sample were... 119A comparison of the Sn-NMR spectra confirmed that they were identical. Both procedures for monitoring compound formation can be used interchangeably, and both are used in the experimental examples.

[0135] Sn6-oxocluster formulation and its use

[0136] In another embodiment, the disclosed and claimed subject matter comprises a formulation comprising (i) one or more disclosed and claimed Sn6-oxoclusters and (ii) one or more solvents suitable for use in a spin coating process. In one embodiment, the formulation comprises (i) two or more disclosed and claimed Sn6-oxoclusters and (ii) one or more solvents suitable for use in a spin coating process.

[0137] In another embodiment, the subject matter disclosed and claimed comprises preparing a target compound in a spin-coating solvent (mixture) at a desired concentration, avoiding the isolation of the material, and directly forming a spin-coating formulation. In one embodiment, such a formulation does not contain toluene.

[0138] In one embodiment, one or more solvents suitable for use in a spin coating process include one or more alcohols, esters, ketones, lactones, diketones, solvents having aromatic moieties, solvents having carboxylic acids, amides, and mixtures thereof.

[0139] In another embodiment, one or more solvents suitable for use in the spin coating process include 1-methoxy-2-propanyl acetate (PGMEA), 1-methoxy-2-propanol (PGME), butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxypropanoate, methyl-3-ethoxypropanoate, methyl-3-methoxypropanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, and ethylene glycoside. Examples include toluene monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, cyclopentyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, toluene, 2-heptanone, 1-hexanol, 4-methyl-2-pentanol, and anisole. In a further embodiment of this embodiment, one or more solvents for use in the spin coating process include one or more of toluene, THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol. In a further embodiment of this embodiment, one or more solvents for use in the spin coating process include one or more of THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol.In one embodiment, such a composition does not contain toluene. In another embodiment, the composition comprises one of 2-heptanone, cyclohexanone, PGMEA, PGME, a mixture of anisole and PGMEA, a mixture of anisole and cyclohexanone, and a mixture of anisole and 2-heptanone.

[0140] In another embodiment, the Sn6-oxocluster formulation has an Sn cluster concentration of about 1 mg / mL to about 1000 mg / mL. In another embodiment, the Sn6-oxocluster can be incorporated into a solution having an Sn cluster concentration of about 1 mg / mL to about 100 mg / mL. In another embodiment, the Sn6-oxocluster can be incorporated into a solution having an Sn cluster concentration of about 1 mg / mL to about 50 mg / mL. In another embodiment, the Sn6-oxocluster can be incorporated into a solution having an Sn cluster concentration of about 10 mg / mL to about 50 mg / mL. In another embodiment, the Sn6-oxocluster formulation has an Sn cluster concentration of about 25 mg / mL to about 50 mg / mL. In another embodiment, the Sn6-oxocluster formulation has an Sn cluster concentration of about 50 mg / mL to about 100 mg / mL.

[0141] The disclosed and claimed subject matter further comprises using the disclosed and claimed Sn6-oxocluster formulations in EUV and electron beam processes. Such formulations may be used or used to pattern a radiosensitive coating in a process comprising: (i) forming a coating on a substrate surface using one or more of the disclosed and claimed Sn6-oxocluster formulations; (ii) drying the coating to produce a dry layer; and (iii) irradiating at least a portion of the dry layer to form a latent image.

[0142] In one embodiment, the substrate of step (i) includes silicon. In one embodiment, the substrate of step i includes silicon and at least one additional material layer (i.e., a stack of material) on which material is deposited.

[0143] In one embodiment, the dried layer in step (ii) has a thickness of about 1 nm to about 500 nm. In one embodiment, the dried layer in step (ii) has a thickness of about 10 nm to about 100 nm. In one embodiment, the dried layer in step (ii) has a thickness of about 15 nm to about 50 nm.

[0144] In one embodiment, the irradiation in step (iii) includes irradiating at least a portion of the dry layer with ionizing radiation. In one embodiment of this embodiment, the ionizing radiation has a wavelength range of about 10 nm to about 365 nm. In one embodiment of this embodiment, the ionizing radiation is generated by an electron beam.

[0145] Method for photopatterning materials: Spin-coating the substrate at 500 rpm / 5 seconds, then spin-coating again at 800-5000 rpm for 15-120 seconds, exposing the wafer through a mask with an electron beam of 2-100 keV at 1-10000 μC or EUV (13.5 nm), baking the exposed wafer at 100-200°C for 0.5-20 minutes, and developing in an organic solvent (mixture) for 15-300 seconds. Examples of solvents and their mixtures include, but are not limited to, 2-heptanone, cyclohexanone, PGMEA, PGME, a mixture of anisole and PGMEA, a mixture of anisole and cyclohexanone, and a mixture of anisole and 2-heptanone.

[0146] It will also be apparent to those skilled in the art that various modifications can be made to how the disclosed subject matter is implemented in accordance with the embodiments described herein, without departing from the spirit and scope of the disclosed subject matter.

[0147] Use as a metal hard mask

[0148] The material is applied by spin coating and then fired to convert the metal precursor film into a MOx film. This film functions as a metal hard mask and can be used in conjunction with other photopatternable resists such as CAR. Optionally, the hard mask material can be patterned using a lithography exposure process. In this case, the metal oxide material is applied by spin coating, followed by a soft baking process, and then irradiated with electromagnetic radiation through the mask. This is followed by another baking process. Optionally, the film is then developed with a solvent to wash away either the exposed or unexposed areas. Alternatively, etching can be applied directly to the film, for example, using an HBr etching gas.

[0149] [Examples]

[0150] Herein, we refer to more specific embodiments of the present disclosure and experimental results supporting such embodiments. The examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter.

[0151] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific examples provided herein without departing from the spirit and scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the descriptions provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claim and its equivalents.

[0152] Materials and methods:

[0153] The disclosed and claimed process utilizes commercially available materials (e.g., THF, PGME, cyclohexanone, toluene, methoxyacetic acid, formic acid, acetic acid, pivalic acid, tetrahydrofuran-2-carboxylic acid (CAS 16874-33-2, 1,3-dithiane-2-carboxylic acid (CAS 20461-89-6), 5-oxo-2-tetrahydrofurancarboxylic acid (CAS 4344-84-7), CDCl3, C6D6)). RSn(OR')3 (R=Me, nBu; R'=tBu, tAmyl) compounds were prepared according to (modified) literature procedures. See F. Banse et al., Inorg. Chem, 34, 6371 (1995).

[0154] Example 1: Preparation of a series of Sn6 drum clusters having methoxyacetate ligands with varying ratios of Me ligands and nBu ligands bonded to Sn atoms.

[0155] General formula of the target compound: [(MeSn) x (nBuSn) 6-x O6(O2CCH2OMe)6].

[0156] Mixtures of two Sn starting materials RSn(OtAmyl)3 (total 1 mmol, 1 equivalent, R=Me and nBu) are weighed into crimped vials (reaction vials) equipped with a stirring rod in a glove box in different ratios of Me:Bu (1:5, 1:2, 1:1, 2:1, 5:1). 4 mL of tetrahydrofuran is added, and the vials are closed. After transferring to a hood, water (0.98 mmol, 3 equivalents) is added by syringe while stirring. In a separate vial, methoxyacetic acid is added. [ka] Dissolve (1 mmol, 1 equivalent) in 5 mL of tetrahydrofuran and slowly add the solution dropwise to the reaction vial using a syringe. Stir the solution overnight, and a clear solution is obtained the next day. Remove all volatile substances using a rotary evaporator (30°C, 1 mbar) to obtain the product as a clear to white solid. The yield values ​​are as follows: [Table 2] Samples of materials isolated from each reaction were individually dissolved in CDCl3 and subjected to NMR measurement. See Figure 1.

[0157] Example 2: Preparation of a series of Sn6 drum clusters having formate ligands with varying ratios of Me ligands and nBu ligands bonded to Sn atoms.

[0158] General formula of the target compound: [(MeSn) x (nBuSn) 6-x [O6(O2CH)6].

[0159] Mixtures of two Sn starting materials RSn(OtAmyl)3 (total 0.326 mmol, 1 equivalent, R=Me and nBu) are weighed into crimped vials (reaction vials) equipped with a stirring rod in a glove box in different ratios of Me:Bu (1:5, 1:2, 1:1, 2:1, 5:1). Add 4 mL of tetrahydrofuran and close the vial. After transferring to a hood, water (0.98 mmol, 3 equivalents) is added by syringe while stirring. In a separate vial, formic acid [ka] Dissolve (0.33 mmol, 1 equivalent) in 5 mL of tetrahydrofuran and slowly add the solution dropwise to the reaction vial using a syringe. Stir the solution overnight. Remove all volatile substances using a rotary evaporator (30°C, 1 mbar) under vacuum to obtain the product as a white solid. The yield values ​​are as follows: [Table 3] Samples of materials isolated from each reaction were individually dissolved in CDCl3 and subjected to NMR measurement. See Figure 2.

[0160] Example 3: Preparation of mixed nBu-Sn6 drum clusters having pivalate and acetate ligands from pure nBu-Sn6 pivalate and acetate drum cluster compounds

[0161] The general formula of the target compound is [(nBuSn)6O6(O2CCH3)3(O2CC(CH3)3)3].

[0162] The starting materials were synthesized according to the procedures described in known literature. [(nBuSn)6O6(O2CCH3)6](200 mg, 132 μmol) was placed in a vial, dissolved in 3 mL of toluene-d8, and stirred for 30 minutes. The resulting solution was filtered through a 0.2 μm syringe filter and transferred to a second vial containing [(nBuSn)6O6(O2CC(CH3)3)6](230 mg, 131 μmol). After stirring the solution for 5 minutes, a sample (0.6 mL) was taken for NMR measurement. The mixture was stirred overnight, and a second sample was taken for NMR measurement. The NMR spectrum was recorded directly from the reaction solution. 119 In the Sn NMR spectrum, characteristic signals were detected at -485 ppm and -486 ppm, along with signal broadening over time. See Figure 3.

[0163] Example 4: Preparation of Me-Sn6 drum clusters using a mixture of tetrahydrofuran-2-carboxylate ligand and 1,3-dithiane-2-carboxylate ligand

[0164] Formula of the target compound: [(MeSn)6O6(O2C(C4H7O))3(O2C(C4H7S2))3].

[0165] Weigh the Sn starting material MeSn(OtAmyl)3 (4.11 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod in a glove box. Add 28 mL of 1-methoxypropan-2-ol and 4.9 mL of cyclohexanone, then close the vial. After transferring to a hood, add water (12.3 mmol, 3 equivalents) with a syringe while stirring. A turbid mixture will be formed. In a separate vial, add the desired acid [ka] Dissolve 2.05 mmol (0.5 equivalents) of each compound in 2 mL of solvent mixture, and slowly add the resulting solution dropwise to the reaction vial using a syringe. Stir the solution overnight. Record the NMR spectrum for the solid isolated after removing the solvent and redissolving in THF-d8. 119 Characteristic signals and signal broadening were detected in the Sn NMR spectrum at -457 ppm and -458 to -459 ppm. See Figure 4.

[0166] Example 5: Preparation of Me-Sn6 drum clusters using a mixture of tetrahydrofuran-2-carboxylate ligand and pivalate ligand

[0167] Formula of the target compound: [(MeSn)6O6(O2C(C4H7O))3(O2CC(CH3)3)3].

[0168] Weigh the Sn starting material MeSn(OtAmyl)3 (0.77 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod in a glove box. Add 8 mL of toluene and close the vial. After transferring to a hood, add water (2.31 mmol, 3 equivalents) with a syringe while stirring. A turbid mixture will be formed. In another vial, add the desired acid [ka] Dissolve 0.39 mmol and 0.5 equivalents of each in 2 mL of toluene, and slowly add the resulting solution dropwise to the reaction vial using a syringe. A clear to slightly cloudy solution will then form. Stir the solution overnight, and a cloudy solution will be obtained the next day. Place 1.5 mL of the homogenized solution into a round-bottom flask and remove all solvent using a rotary evaporator. Redissolve the isolated white solid in 0.7 CDCl3 and subject it to NMR measurement. 119 For a comparison of Sn NMR spectra, please refer to Figure 5. 119In the Sn NMR spectrum, characteristic signals were detected at -463 ppm and -465 ppm. The solution sample was diluted in THF and the mass spectrum was recorded. The detected mixed ligand cluster species are listed in Table 4. [Table 4]

[0169] Example 6: Preparation of Me-Sn6 drum clusters using a mixture of 5-oxo-2-tetrahydrofurancarboxylate ligand and formate ligand

[0170] Formula of the target compound: [(MeSn)6O6(O2CH)3(O2C(C4H5O2))3].

[0171] Weigh the Sn starting material MeSn(OtAmyl)3 (3.34 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 9 mL of 1-methoxypropan-2-ol and 9 mL of cyclohexanone to obtain a clear solution. In the next step, add water (10 mmol, 3 equivalents) with a syringe while stirring. A turbid solution is formed. In separate vials, add the desired acid [ka] Dissolve (1.67 mmol, 0.5 equivalents each) in 1 mL of the solvent mixture and slowly add it dropwise to the reaction vial using a syringe. Stir the turbid solution overnight, and a clear solution will be obtained the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 A characteristic cluster signal at -458 ppm was detected in the Sn NMR spectrum.

[0172] Example 7: Preparation of Me-Sn6 drum clusters using a mixture of 5-oxo-2-tetrahydrofuran carboxylate ligand and tetrahydrofuran-2-carboxylate ligand

[0173] Formula of the target compound: [(MeSn)6O6(O2CH)3(O2C(C4H5O2))3(O2C(C4H7O))3].

[0174] Weigh the Sn starting material MeSn(OtAmyl)3 (4.41 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 24 mL of 1-methoxypropan-2-ol and 24 mL of cyclohexanone to obtain a clear solution. In the next step, add water (13.22 mmol, 3 equivalents) with a syringe while stirring. In separate vials, add the desired acid. [ka] Dissolve (2.2 mmol, 0.5 equivalents each) in 2 mL of solvent mixture and slowly add it dropwise to the reaction vial using a syringe. Stir the solution overnight. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 Characteristic signals were detected at -459 ppm and -462 ppm in the Sn NMR spectrum.

[0175] Example 8: Preparation of Sn6 drum clusters using Me ligands and iPr ligands bonded to Sn atoms, and a mixture of tetrahydrofuran-2-carboxylate ligand and formate ligand.

[0176] Formula of the target compound: [(MeSn)5(iPrSn)1O6(O2CH)3(O2C(C4H7O))3].

[0177] Weigh the Sn starting materials MeSn(OtAmyl)3 (1.42 mmol, 5 equivalents) and iPrSn(OtAmyl)3 (0.28 mmol, 1 equivalent) into crimped vials (reaction vials) equipped with a stirring bar, and close the vials in a glove box. After transferring to a hood, add 9 mL of 1-methoxypropan-2-ol and 9 mL of cyclohexanone to obtain a clear solution. In the next step, add water (5.12 mmol, 18 equivalents) with a syringe while stirring. In separate vials, add the desired acid. [ka] Dissolve (0.85 mmol, 3 equivalents each) in 1 mL of solvent mixture and slowly add it dropwise to the reaction vial using a syringe. Stir the clear solution overnight. Concentrate 4 mL of the sample to approximately 1 mL, and then use a capillary insert containing C6D6 for locking. 119 It was used for Sn-NMR measurements. 119 In the Sn NMR spectrum, characteristic signals were detected at -460 ppm (Me-Sn) and -502 ppm (iPr-Sn).

[0178] Example 9: Preparation of Sn6 drum clusters having tetrahydrofuran-3-carboxylate ligands in which Me ligands and nBu ligands are bonded to Sn atoms within the same cluster.

[0179] The general formula of the target compound is [(MeSn)3(nBuSn)3O6(O3C5H7)6].

[0180] A mixture of two Sn starting materials, MeSn(OtBu)3 (0.69 mmol, 244 mg) and nBuSn(OtAmyl)3 (0.69 mmol, 302 mg), is weighed into a crimped vial equipped with a stirring rod in a glove box, and the vial is closed. After transferring to a hood, 9 mL of cyclohexanone is added. While stirring, water (4.15 mmol, 3 equivalents) is added by syringe. In a separate vial, tetrahydrofuran-3-carboxylic acid is added. [ka] Dissolve (1.38 mmol, 1 equivalent) in 1 mL of cyclohexanone, and slowly add the solution dropwise to the reaction vial using a syringe. Stir the solution overnight, and a clear solution will be obtained the next day. 1D and 2D 119 For Sn-NMR measurement, the sample is collected using a capillary insert containing C6D6 for locking. The mass spectrometry sample is prepared by diluting the reaction mixture in THF. Figure 10 shows: 119 Sn- 119 The Sn-inadequate NMR spectrum is shown. This technique detects bonds between individual Sn atoms. The observed coupling demonstrates the presence of both MeSn and nBuSn fragments within the same molecule. The Me-Sn signal is detected at -463 ppm, and the nBu-Sn signal is detected at -484 ppm.

[0181] Figure 11 shows an overview of the recorded mass spectra and a comparison with the simulated isotopic patterns for the cluster species listed in Table 5. The following cluster species were detected by mass spectrometry. [Table 5]

[0182] Example 10: Preparation of Me-Sn6 drum clusters using a mixture of 5-oxo-2-tetrahydrofurancarboxylate ligand and formate ligand

[0183] Formula of the target compound: [(MeSn)6O6(O2CH)2(O2C(C4H5O2))4].

[0184] Weigh the Sn starting material MeSn(OtBu)3 (3.98 mmol, 1 equivalent) into a 100 mL round-bottom nitrogen flask (reaction flask) equipped with a stirring bar, and add 44 mL of THF to obtain a clear solution. Close the flask, transfer it to a hood, and connect it to an inert gas line. Acid [ka] (2.65 mmol, 0.67 equivalents) and [ka] Dissolve (1.31 mmol, 0.33 equivalents) in 6 mL of THF and slowly add it dropwise to the reaction flask using a syringe. Stir the turbid solution overnight, and a clear solution will be obtained the next day. Remove all volatile substances under vacuum to obtain the product as a white powder. Dissolve the sample in dry cyclohexanone and lock it using a capillary insert containing C6D6. 119 Used for Sn-NMR measurements. 119 A characteristic signal at -456 ppm was detected in the Sn NMR spectrum.

[0185] Example 11: Preparation of Me-Sn6 drum clusters using a mixture of 5-oxo-2-tetrahydrofurancarboxylate ligand and formate ligand

[0186] Formula of the target compound: [(MeSn)6O6(O2CH)3(O2C(C4H5O2))3].

[0187] Weigh the Sn starting material MeSn(OtBu)3 (8.4 mmol, 1 equivalent) into a 100 mL round-bottom nitrogen flask (reaction flask) equipped with a stirring bar, and add 96 mL of cyclohexanone to obtain a clear solution. Close the flask, transfer it to a hood, and connect it to an inert gas line. Acid [ka] (4.2 mmol, 0.5 equivalent) and [ka] Dissolve (4.2 mmol, 0.5 equivalents) in 4 mL of cyclohexanone and slowly add it dropwise to the reaction flask using a syringe. Stir the turbid solution overnight, and a clear solution will be obtained the next day. For NMR measurement, collect the sample using a capillary insert containing a C6D6 lock. 119A characteristic signal at -459 ppm was detected in the Sn NMR spectrum. The final reaction solution was characterized by mass spectrometry, confirming the presence of a ligand mixture within the cluster. Figure 12 shows an overview of the recorded mass spectrum and a comparison with the simulated isotopic patterns for the mixed ligand cluster species listed in Table 6. [Table 6]

[0188] Example 12: Preparation of Me-Sn6 drum clusters using a mixture of 2,2-dimethyl-5-oxo-2-tetrahydrofurancarboxylate ligand and formate ligand

[0189] Formula of the target compound: [(MeSn)6O6(O2CH)2(O2C(C6H9O2))4].

[0190] Weigh the Sn starting material MeSn(OtAmyl)3 (2.2 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 25 mL of cyclohexanone to obtain a clear solution. In the next step, add water (26.7 mmol, 3 equivalents) with a syringe while stirring. A turbid solution is formed. In another vial, add the desired acid [ka] (1.5 mmol, 0.67 equivalents) and [ka] Dissolve (0.7 mmol, 0.33 equivalents) in 5 mL of cyclohexanone and slowly add it dropwise to the reaction vial using a syringe. Stir the turbid solution overnight, and a clear solution will be obtained the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 A characteristic signal at -459 ppm was detected in the Sn NMR spectrum.

[0191] Example 13: Preparation of nBu-Sn6 drum clusters using a mixture of lipoate ligand and 3-maleimide propionate ligand

[0192] Formula of the target compound: [(MeSn)6O6(O2C(CH2)2(NC4O2H2))3(O2C(CH2)4(C3H5S2))3].

[0193] Weigh the Sn starting material nBuSn(OtAmyl)3 (2.1 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 36 mL of cyclohexanone to obtain a clear solution. In the next step, add water (6.3 mmol, 3 equivalents) with a syringe while stirring. A clear solution is formed. In another vial, add the desired acid [ka] (1.1 mmol, 0.5 equivalents) and [ka] Dissolve (1.1 mmol, 0.5 equivalents) in 4 mL of solvent and slowly add it dropwise to the reaction vial using a syringe. Stir the clear solution overnight, and a clear solution will be obtained the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 Characteristic signals were detected at -484 ppm and -485 ppm in the Sn NMR spectrum.

[0194] Example 14: Preparation of nBu-Sn6 drum clusters using a mixture of acetate ligand and lipoate ligand

[0195] Formula of the target compound: [(nBuSn)6O6(O2CCH3)] 4.8 (O2C(CH2)4(C3H5S2)) 1.2 ].

[0196] Weigh the Sn starting material nBuSn(OtAmyl)3 (2.9 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 38 mL of cyclohexanone to obtain a clear solution. In the next step, add water (8.5 mmol, 3 equivalents) with a syringe while stirring. A clear solution is formed. In another vial, add the desired acid [ka] (2.3 mmol, 0.8 equivalents) and [ka] Dissolve (0.6 mmol, 0.2 equivalents) in 4 mL of solvent and slowly add it dropwise to the reaction vial using a syringe. Stir the clear solution overnight, and a clear solution will be obtained the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 In the Sn NMR spectrum, characteristic signals were detected at -486.0 ppm and -486.8 ppm. The mixed ligand cluster species detected by mass spectrometry are listed in Table 7. [Table 7]

[0197] Example 15: Preparation of nBu-Sn6 drum clusters using a mixture of 3-maleimidepropionate ligand and 2THF-carboxylate ligand.

[0198] Formula of the target compound: [(MeSn)6O6(O2C(CH2)2(NC4O2H2))3(O2C(C4H7O)3].

[0199] Weigh the Sn starting material MeSn(OtBu)3 (2.1 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 28 mL of cyclohexanone to obtain a clear solution. In the next step, add water (6.2 mmol, 3 equivalents) with a syringe while stirring. A turbid solution is formed. In another vial, add the desired acid [ka] (1.0 mmol, 0.5 equivalents) and [ka] Dissolve (1.0 mmol, 0.5 equivalents) in 2 mL of solvent and slowly add it dropwise to the reaction vial using a syringe. Stir the turbid solution overnight, and a clear solution will be obtained the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 Characteristic signals were detected at -462 ppm and -464 ppm in the Sn NMR spectrum.

[0200] Example 16: Preparation of Sn6 drum clusters using a mixture of Me- units and nBu-Sn units, and a mixture of lipoate ligands and acetate ligands.

[0201] Formula of the target compound: [(MeSn)3(nBuSn)3O6(O2C(CH2)4(C3H5S2))3(O2CCH3)3].

[0202] Weigh the Sn starting materials MeSn(OtBu)3 (0.7 mmol, 1 equivalent) and nBuSn(OtAmyl)3 (0.7 mmol, 1 equivalent) into a crimped vial (reaction vial) equipped with a stirring rod, and close the vial in a glove box. After transferring to a hood, add 16 mL of cyclohexanone to obtain a clear solution. In the next step, add water (4.4 mmol, 6 equivalents) with a syringe while stirring. A turbid solution is formed. In a separate vial, add the desired acid [ka] (0.7 mmol, 1 equivalent) and [ka] Dissolve (0.7 mmol, 1 equivalent) separately in 2 mL of solvent and slowly add it dropwise to the reaction vial using a syringe. Stir the solution overnight, and a clear solution will be obtained the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 Characteristic signals were detected at -465 ppm and -487 ppm in the Sn NMR spectrum. Figure 13 shows an overview of the recorded mass spectrum and a comparison with the simulated isotopic patterns for the mixed ligand cluster species listed in Table 8. [Table 8]

[0203] Example 17: Preparation of nBu-Sn6 drum clusters using a mixture of 1,2-dithiolane-4-carboxylate ligand and 3THF-carboxylate ligand

[0204] Formula of the target compound: [(nBuSn)6O6(O2C(C3H5S2))3(O2C(C4H7O)3].

[0205] The Sn starting material nBuSn(OtAmyl)3 (0.55 mmol, 1 equivalent) is weighed into a crimped vial (reaction vial) equipped with a stirring rod, and the vial is closed in a glove box. After transferring to a hood, 5 mL of cyclohexanone is added to obtain a clear solution. In the next step, water (1.66 mmol, 3 equivalents) is added with a syringe while stirring. A clear solution is formed. In the other vial, [ka] Dissolve (0.28 mmol, 0.5 equivalents) in 1.7 mL of toluene and dilute with 0.8 mL of cyclohexanone. In another vial, [ka] Dissolve (0.28 mmol, 0.5 equivalents) in 2 mL of cyclohexanone. Slowly add both carboxylic acid solutions dropwise to the reaction vial using a syringe. Stir the solution overnight to obtain a clear solution the next day. Using a capillary insert containing C6D6 for locking, 119 A sample is collected for Sn-NMR measurement. 119 Characteristic signals were detected at -465 ppm and -487 ppm in the Sn NMR spectrum.

[0206] Comparative Test 1: Solubility Test

[0207] Pure and mixed Sn6 clusters were prepared at different target concentrations in a cyclohexanone / 1-methoxy-2-propanol (1 / 1) solvent mixture according to Example 6. Cyclohexanone and 1-methoxy-2-propanol are commonly accepted industrial solvents. The solubility of each cluster was determined by visual observation of the mixture. Precipitation formation indicates that the solubility product of the species present in the solution was exceeded. These results are R a A pure Sn6 drum cluster material that is =Me and has a formate ligand or acetate ligand is insoluble in a solvent mixture at any given concentration, whereas R a The fact that =nBu and the sample has an acetate ligand indicates that the solubility requirement is not met at 20 g / L. a or R b Introducing a mixed ligand to either of these significantly increases the solubility of the compound, making the resulting solution suitable for coating purposes. [Table 9]

[0208] Comparative Test 2: Electron Sensitivity of Sn6 Drum Clusters Containing Formate and Acetate Ligands Compared to Pure Ligand Clusters and Mixed Ligand Clusters

[0209] The [[(nBuSn)6O6(O2CCH3)6] formulation was prepared by dissolving a solid material synthesized by a procedure known in the literature in toluene. See Chandrasekhar et al., Inorg. Chem., 26, 1050 (1987). [(nBuSn)6O6(O2CH)6] was prepared according to Example 5, using cyclohexanone instead of toluene as the solvent. All formulations of the mixed ligand Sn6 drum compounds were prepared according to the above procedure, although the target concentration of the cluster compound was on a different scale of 20 g / L (see Examples 4, 6-8).

[0210] Wafer preparation and electron beam irradiation procedure

[0211] The silicon wafer was cleaned with oxygen plasma for 10 minutes. Then, each solution was spin-coated onto the wafer at 500 rpm for 5 seconds, followed by 30 seconds at 800-4000 rpm cycles. Next, a soft bake at 100°C was performed for 120 seconds, yielding films with thicknesses of 25-35 nm, as measured by an ellipsometer. The wafer was then divided into 1 × 1 cm pieces and subjected to a temperature of 1-5000 μC / cm². 2 Electron beam irradiation was performed within the specified dose range, with an acceleration voltage of 30 keV and a working distance of 4 mm. The resist was then developed in 2-heptanone at room temperature for 120 seconds and dried under nitrogen for 60 seconds. The structure was then determined by profilometry, and the peak height relative to the dose was converted into a fitted dose-level curve. 50 The value is defined as the exposure level at which 50% of the film thickness of the fully cured material is retained after development. This value is used as an indicator of the sensitivity performance of a given material.

[0212] Sensitivity comparison of Sn6 drum clusters containing acetate ligands in electron beam irradiation experiments.

[0213] D of [(nBuSn)6O6(O2CCH3)6], [(MeSn)6O6(O2CCH3)3(O2CC4H5O2)3] and [(MeSn)6O6(O2CCH3)3(O2CC4H7O)3] 50 The values ​​are 251, 178, and 156 μC / cm², respectively. 2 Compared to the reference compound [(nBuSn)6O6(O2CCH3)6] which does not contain mixed ligands, the acetate containing mixed clusters shows a clear increase in electron beam sensitivity.

[0214] Sensitivity comparison of Sn6 drum clusters containing formate ligands in electron beam irradiation experiments.

[0215] D of [(nBuSn)6O6(O2CH)6], [(MeSn)6O6(O2CH)3(O2CCH2OCH3)3], [(MeSn)6O6(O2CH)3(O2CC4H5O2)3] and [(MeSn)6O6(O2CH)3(O2C(CHS2C3H6))3] 50 The values ​​are 178, 50, 73, and 57 μC / cm², respectively. 2 Compared to the [(nBuSn)6O6(O2CH)6] cluster, the electron beam sensitivity of the mixed cluster containing formyl is clearly increased.

[0216] Comparative Test 3: EUV Sensitivity and Patterning of Sn6 Drum Clusters

[0217] The [(nBuSn)6O6(O2CCH3)6] formulation was prepared by dissolving a solid material synthesized by a procedure known in the literature in toluene. See Chandrasekhar et al., Inorg. Chem., 26, 1050 (1987). [(nBuSn)6O6(O2CH)6] was prepared according to Example 5, using cyclohexanone instead of toluene as the solvent. All formulations of the mixed ligand Sn6 drum compound were prepared according to the above procedure, although at different scales with a target concentration of 20 g / L for the cluster compound (see Examples 4, 6-8).

[0218] Coating and EUV exposure experiments were conducted at the Paul-Scherrer-Institute in Switzerland. The formulation was deposited onto a 4-inch silicon wafer by spin coating at a final spin velocity in the range of 800–4000 rpm. After coating, the film was baked at 100°C for 120 seconds. The resulting film was irradiated with EUV (13.5 nm) radiation through an interference mask and developed in 2-heptanone for 120 seconds. The critical dimension (CD) and linewidth roughness (LWR) were measured by image analysis using the open-source software SMILE. Next, the dose-to-gel structure was determined by profilometry, and the peak height relative to the dose was converted into a fitted dose-level curve. [Table 10]

[0219] The mixed cluster ligand Sn6 drum compounds showed improved dose-to-size compared to [(nBuSn)6O6(O2CCH3)6] and [(nBuSn)6O6(O2CH)6] which did not contain the mixed ligand. [(MeSn)6O6(O2CH)3(O2CC4H5O2)3] showed improved gelation dose and LWR compared to [(nBuSn)6O6(O2CCH3)6] and [(nBuSn)6O6(O2CH)6]. Line-space patterns were obtained for all materials. SEM images of the patterns are shown in Figures 6 to 9.

[0220] Although the present invention has been described and illustrated in some detail, this disclosure is for illustrative purposes only, and those skilled in the art will understand that numerous changes can be made to the conditions and order of the steps without departing from the spirit and scope of the invention.

Claims

1. formula: [(R ａ１ Sn)(R ａ２ Sn)(R ａ３ Sn)(R ａ４ Sn)(R ａ５ Sn)(R ａ６ Sn)]O ６ [(O ２ C-R ｂ１ )(O ２ C-R ｂ２ )(O ２ C-R ｂ３ )(O ２ C-R ｂ４ )(O ２ C-R ｂ５ )(O ２ C-R ｂ６ )] [In the formula, (A)R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Each of these is an unsubstituted linear C １ ~C １０ Linear carbon atoms substituted with alkyl groups or halogens １ ~C ６ Linear carbon chains substituted with alkyl or amino groups １ ~C ６ Alkyl alkyl group, C ５ ~C ６ Linear carbon chain substituted with unsubstituted aromatic groups １ ~C ６ Alkyl alkyl, unsubstituted branched C ３ ~C １０ Branched C cells substituted with alkyl groups and halogens ３ ~C １０ Alkyl alkyl group, C １ ~C １０ Heteroalkyl groups, branched C groups substituted with amino groups ３ ~C １０ Alkyl alkyl groups, unsubstituted amines, substituted amines, -Si(CH ３ ) ３ , benzyl group, C ３ ~C ８ Unsubstituted cyclic alkyl groups, halogen-substituted C ３ ~C ８ Cyclic alkyl groups, C substituted with amino groups ３ ~C ８ Cyclic alkyl group, C ４ ~C ８ Unsubstituted aromatic groups, halogen-substituted C ４ ~C ８ C substituted with aromatic groups and amino groups ４ ~C ８ aromatic group, C ３ ~C １０ Heterocyclic groups, unsubstituted linear carbon chains ２ ~C １０ Alkenyl group, unsubstituted branched carbon ３ ~C １０ Alkenyl group, unsubstituted linear C ２ ~C １０ Alkynyl group and unsubstituted branched C ４ ~C １０ Individually selected from the group consisting of alkynyl groups; (B) R ｂ１ 、R ｂ２ 、R ｂ３ 、R ｂ４ 、R ｂ５ and R ｂ６ each of which is H; unsubstituted straight-chain C １ ~C １０ alkyl group; -CN group, -OH group, -OR' group, -SR' group or -S-S-R' group (wherein, R' is a straight-chain or branched C １ ~C ４ alkyl group), -C(=O)OR'' group (wherein, R'' is a straight-chain or branched C １ ~C ４ alkyl group), -NO ２ group, halogen or -C(=O)H group, a substituted straight-chain C １ ~C １０ alkyl group substituted with one or more of; unsubstituted branched C ３ ~C １０ alkyl group; -CN group, -OH group, -OR' group, -SR' group or -S-S-R' group (wherein, R' is a straight-chain or branched C １ ~C ４ alkyl group), -C(=O)OR'' group (wherein, R'' is a straight-chain or branched C １ ~C ４ alkyl unit), -NO ２ group, halogen or -C(=O)H group, a substituted branched C ３ ~C １０ alkyl group; C ３ ~C ８ unsubstituted cyclic alkyl group; straight-chain C ２ ~C １０ alkenyl group; branched C ３ ~C １０ alkenyl group, 5-membered heterocyclic ring, and 6-membered heterocyclic ring; 【Chemistry 1】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 2】 Base (where n = 1 to 4 in the formula), 【Transformation 3】 Base (where n = 1 to 4 in the formula); 【Chemistry 4】 Base (where n = 1 to 6 in the formula); 【Transformation 5】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Transformation 6】 group (wherein each R ｍ The group consists of H and linear C. １ ~C ４ Chain, or branch C ３ ~C ４ (Selected independently of the chain); 【Transformation 7】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ It is an alkylene group; and (C)(i)R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ At least one of them is R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Unlike the rest of the and / or (ii)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ At least one of them is R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ [Different from the rest] Tin cluster.

2. R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ At least one of them is R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ A tin cluster according to claim 1, which is different from the others among them.

3. R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ At least one of them is R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ A tin cluster according to claim 1, which is different from the others among them.

4. R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ At least one of them is R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Unlike the others, R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ At least one of them is R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ A tin cluster according to claim 1, which is different from the others among them.

5. (A)R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Each of these is an unsubstituted linear C １ ~C ４ Alkyl alkyl, unsubstituted branched C ３ ~C ４ Alkyl alkyl group, C ２ ~C ６ Alkenyl group and C ４ ~C ６ The tin cluster according to claim 1, individually selected from the group consisting of unsubstituted aromatic groups.

6. (A)R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Each of them is -CH ３ Base, -CH(CH ３ ) ２ group, -C(CH ３ ) ３ Base, -CH=CH ２ group, -CH ２ CH=CH ２ group, -CH ２ CH ２ CH=CH ２ group, -CH ２ CH ２ CH ２ CH ３ group, -C ６ H ５ The group and -CH ２ -C ６ H ５ A tin cluster according to claim 1, individually selected from a group consisting of groups.

7. (A)R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Each of them is -CH ３ Base, -CH(CH ３ ) ２ Base, -CH=CH ２ The base, and -CH ２ CH ２ CH ２ CH ３ A tin cluster according to claim 1, individually selected from a group consisting of groups.

8. (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of them, -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituted linear carbon group (C) substituted with one or more of the following: C, halogen, or -C(=O)H group １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched carbon (C) substituted with one or more of the following: a group, halogen, or -C(=O)H group. ３ ~C ６ Alkyl alkyl group; C ３ ~C ６ Unsubstituted cyclic alkyl groups; linear C ２ ~C ６ Alkenyl group; branched C ３ ~C ６ Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; 【Transformation 8】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 9】 Base (where n = 1 to 4 in the formula), 【Chemistry 10】 Base (where n = 1 to 4 in the formula); 【Chemistry 11】 Base (where n = 1 to 6 in the formula); 【Chemistry 12】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 13】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 14】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 1, wherein the group is an alkylene group.

9. (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituting linear carbon chains with one or more of the following groups: a group or a -C(=O)H group. １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched C12C ３ ~C ６ Alkyl group; linear C chain ２ ~C ６ Alkenyl group; branched C ３ ~C ６ Alkenyl group, 【Chemistry 15】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 16】 Base (where n = 1 to 4 in the formula); 【Chemistry 17】 Base (where n = 1 to 6 in the formula); [Chemistry 18] Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 19】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 20】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 1, wherein the group is an alkylene group.

10. (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OR' group (wherein R' is a linear or branched C) １ ~C ４ (which is an alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ A substituted linear C molecule (which is an alkyl group) １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OR' group (wherein R' is a linear or branched C) １ ~C ４ (which is an alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ Substitutive branched C (which is an alkyl unit) ３ ~C ６ alkyl group; 【Chemistry 21】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 22】 Base (where n = 1 to 4 in the formula); 【Chemistry 23】 Base (where n = 1 to 6 in the formula); 【Chemistry 24】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 25】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 26】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 1, wherein the group is an alkylene group.

11. (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, or -OR' group (wherein R' is a linear or branched C) １ ~C ４ A substituted linear C molecule (which is an alkyl group) １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, or -OR' group (wherein R' is a linear or branched C) １ ~C ４ Substitutive branched C (which is an alkyl group) ３ ~C ６ alkyl group; 【Chemistry 27】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 28】 Base (where n = 1 to 6 in the formula); 【Chemistry 29】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Transformation 30】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 31】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 1, wherein the group is an alkylene group.

12. (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of them is -H, 【Chemistry 32】 A tin cluster according to claim 1, individually selected from the group consisting of the following.

13. (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of them is -H, 【Transformation 33】 A tin cluster according to claim 1, individually selected from the group consisting of the following.

14. (A)R ａ１ , R ａ２ , R ａ３ , R ａ４ , R ａ５ and R ａ６ Each of them is -CH ３ Base, -CH(CH ３ ) ２ Base, -CH=CH ２ The base, and -CH ２ CH ２ CH ２ CH ３ Individually selected from a group consisting of groups, (B)R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ Each of them is -H, 【Transformation 34】 A tin cluster according to claim 1, individually selected from the group consisting of the following.

15. formula: [(R ａ（ｉ） Sn) ６－ｘ (R ａ（ｉｉ） Sn) ｘ ]O ６ [(O ２ C-R ｂ（ｉ） ) ６－ｙ (O ２ C-R ｂ（ｉｉ） ) ｙ ] [In the formula, (A)(i)R ａ（ｉ） ≠R ａ（ｉｉ） (ii)R ａ（ｉ） and R ａ（ｉｉ） These are, respectively, unsubstituted linear C １ ~C １０ Linear carbon atoms substituted with alkyl groups or halogens １ ~C ６ Linear carbon chains substituted with alkyl or amino groups １ ~C ６ Alkyl alkyl group, C ５ ~C ６ Linear carbon chain substituted with unsubstituted aromatic groups １ ~C ６ Alkyl alkyl, unsubstituted branched C ３ ~C １０ Branched C cells substituted with alkyl groups and halogens ３ ~C １０ Alkyl alkyl group, C １ ~C １０ Heteroalkyl groups, branched C groups substituted with amino groups ３ ~C １０ Alkyl alkyl groups, unsubstituted amines, substituted amines, -Si(CH ３ ) ３ , benzyl group, C ３ ~C ８ Unsubstituted cyclic alkyl groups, halogen-substituted C ３ ~C ８ Cyclic alkyl groups, C substituted with amino groups ３ ~C ８ Cyclic alkyl group, C ４ ~C ８ Unsubstituted aromatic groups, halogen-substituted C ４ ~C ８ C substituted with aromatic groups and amino groups ４ ~C ８ aromatic group, C ３ ~C １０ Heterocyclic groups, unsubstituted linear carbon chains ２ ~C １０ Alkenyl group, unsubstituted branched carbon ３ ~C １０ Alkenyl group, unsubstituted linear C ２ ~C １０ Alkynyl group and unsubstituted branched C ４ ~C １０ Individually selected from the group consisting of alkynyl groups; (B)(i)R ｂ（ｉ） ≠R ｂ（ｉｉ） (ii)R ｂ（ｉ） and R ｂ（ｉｉ） H; unsubstituted linear C １ ~C １０ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituted linear carbon group (C) substituted with one or more of the following: C, halogen, or -C(=O)H group １ ~C １０ Alkyl alkyl group; unsubstituted branched C ３ ~C １０ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched carbon (C) substituted with one or more of the following: a group, halogen, or -C(=O)H group. ３ ~C １０ Alkyl alkyl group; C ３ ~C ８ Unsubstituted cyclic alkyl groups; linear C ２ ~C １０ Alkenyl group; branched C ３ ~C １０ Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; 【Chemistry 35】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Transformation 36】 Base (where n = 1 to 4 in the formula), 【Chemistry 37】 Base (where n = 1 to 4 in the formula); 【Transformation 38】 Base (where n = 1 to 6 in the formula); 【Chemistry 39】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 40】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 41】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ It is an alkylene group; and (C) (i) x and y are each independently equal to an integer between 1 and 5, or (ii) one of x or y is 0 and the other of x or y is an integer between 1 and 5.

16. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of these is an unsubstituted linear C １ ~C ４ Alkyl alkyl, unsubstituted branched C ３ ~C ４ Alkyl alkyl groups, unsubstituted linear C chains ２ ~C ６ Alkenyl group, unsubstituted branched carbon ３ ~C ６ Alkenyl group and C ４ ~C ６ The tin cluster according to claim 15, individually selected from the group consisting of unsubstituted aromatic groups.

17. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of them is -CH ３ Base, -CH(CH ３ ) ２ group, -C(CH ３ ) ３ Base, -CH=CH ２ group, -CH ２ CH=CH ２ group, -CH ２ CH ２ CH=CH ２ group, -CH ２ CH ２ CH ２ CH ３ group, -C ６ H ５ The base, and -CH ２ -C ６ H ５ A tin cluster according to claim 15, individually selected from a group consisting of groups.

18. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of them is -CH ３ Base, -CH(CH ３ ) ２ Base, -CH=CH ２ The base, and -CH ２ CH ２ CH ２ CH ３ A tin cluster according to claim 15, individually selected from a group consisting of groups.

19. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituted linear carbon group (C) substituted with one or more of the following: C, halogen, or -C(=O)H group １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched carbon (C) substituted with one or more of the following: a group, halogen, or -C(=O)H group. ３ ~C ６ Alkyl alkyl group; C ３ ~C ６ Unsubstituted cyclic alkyl groups; linear C ２ ~C ６ Alkenyl group; branched C ３ ~C ６ Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; 【Chemistry 42】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 43】 Base (where n = 1 to 4 in the formula), 【Chemistry 44】 Base (where n = 1 to 4 in the formula); 【Chemistry 45】 Base (where n = 1 to 6 in the formula); 【Chemistry 46】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 47】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 48】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 15, wherein the group is an alkylene group.

20. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituting linear carbon chains with one or more of the following groups: a group or a -C(=O)H group. １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched C12C ３ ~C ６ Alkyl group; linear C chain ２ ~C ６ Alkenyl group; branched C ３ ~C ６ Alkenyl group, 【Chemistry 49】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); [Transformation 50] Base (where n = 1 to 4 in the formula); 【Chemistry 51】 Base (where n = 1 to 6 in the formula); 【Chemistry 52】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 53】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 54】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 15, wherein the group is an alkylene group.

21. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OR' group (wherein R' is a linear or branched C) １ ~C ４ (which is an alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ A substituted linear C molecule (which is an alkyl group) １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OR' group (wherein R' is a linear or branched C) １ ~C ４ (which is an alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ Substitutive branched C (which is an alkyl unit) ３ ~C ６ alkyl group; 【Transformation 55】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Transformation 56】 Base (where n = 1 to 4 in the formula); 【Chemistry 57】 Base (where n = 1 to 6 in the formula); 【Transformation 58】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 59】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Transformation 60】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 15, wherein the group is an alkylene group.

22. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, or -OR' group (wherein R' is a linear or branched C) １ ~C ４ A substituted linear C molecule (which is an alkyl group) １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, or -OR' group (wherein R' is a linear or branched C) １ ~C ４ Substitutive branched C (which is an alkyl group) ３ ~C ６ alkyl group; 【Chemistry 61】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Transformation 62】 Base (where n = 1 to 6 in the formula); 【Transformation 63】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 64】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Transformation 65】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 15, wherein the group is an alkylene group.

23. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them is -H, 【Chemical Formula 66】 A tin cluster according to claim 15, individually selected from the group consisting of the following.

24. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them is -H, 【Transformation 67】 A tin cluster according to claim 15, individually selected from the group consisting of the following.

25. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of them is -CH ３ Base, -CH(CH ３ ) ２ Base, -CH=CH ２ The base, and -CH ２ CH ２ CH ２ CH ３ Individually selected from a group consisting of groups, (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them is -H, 【Transformation 68】 A tin cluster according to claim 15, individually selected from the group consisting of the following.

26. Formula: [(R ａ（ｉ） Sn) ６－ｘ (R ａ（ｉｉ） Sn) ｘ ]O ６ (O ２ CR-R ｂ（ｉ） ) ｙ [In the equation, x = integers from 1 to 5, y = 6, R ａ（ｉ） and R ａ（ｉｉ） The ratio of R ａ（ｉ） : R ａ（ｉｉ） The tin cluster according to claim 15, having the ratio = (5 - u): (1 + u) (wherein u = an integer from 0 to 4).

27. Formula: (R ａ（ｉ） Sn) ｘ O ６ [(O ２ CR-R ｂ（ｉ） ) ６－ｙ (O ２ CR-R ｂ（ｉｉ） ) ｙ [In the equation, x = 6, y = integers from 1 to 5, R ｂ（ｉ） and R ｂ（ｉｉ） The ratio of R ｂ（ｉ） : R ｂ（ｉｉ） The tin cluster according to claim 15, having the ratio = (5 - p): (1 + p) (where p = an integer from 0 to 4).

28. Formula: [(R ａ（ｉ） Sn) ６－ｘ (R ａ（ｉｉ） Sn) ｘ ]O ６ [(O ２ CR-R ｂ（ｉ） ) ６－ｙ (O ２ CR-R ｂ（ｉｉ） ) ｙ [In the formula, x = 6 or an integer from 1 to 5, y = an integer from 1 to 5, R ａ（ｉ） and R ａ（ｉｉ） The ratio of R ａ（ｉ） : R ａ（ｉｉ） = (5 - u): (1 + u) (where u = an integer from 0 to 4), and R ｂ（ｉ） and R ｂ（ｉｉ） The ratio of R ｂ（ｉ） : R ｂ（ｉｉ） The tin cluster according to claim 15, having the ratio = (5 - p): (1 + p) (where p = an integer from 0 to 4).

29. The tin cluster according to claim 15, including the tin cluster shown in Table 1. Table 1-1 Table 1-2 Table 1-3

30. A mixture of tin clusters comprising two or more tin clusters as described in any one of claims 1 to 29.

31. A mixture of tin clusters comprising two or more tin clusters as shown in Table 1, as described in claim 29.

32. formula: [(R ａ（ｉ） Sn) ６－ｘ (R ａ（ｉｉ） Sn) ｘ ]O ６ [(O ２ C-R ｂ（ｉ） ) ６－ｙ (O ２ C-R ｂ（ｉｉ） ) ｙ ] [In the formula, (A)(i)R ａ（ｉ） ≠R ａ（ｉｉ） (ii)R ａ（ｉ） and R ａ（ｉｉ） These are, respectively, unsubstituted linear C １ ~C １０ Linear carbon atoms substituted with alkyl groups or halogens １ ~C ６ Linear carbon chains substituted with alkyl or amino groups １ ~C ６ Alkyl alkyl group, C ５ ~C ６ Linear carbon chain substituted with unsubstituted aromatic groups １ ~C ６ Alkyl alkyl, unsubstituted branched C ３ ~C １０ Branched C cells substituted with alkyl groups and halogens ３ ~C １０ Alkyl alkyl group, C １ ~C １０ Heteroalkyl groups, branched C groups substituted with amino groups ３ ~C １０ Alkyl alkyl groups, unsubstituted amines, substituted amines, -Si(CH ３ ) ３ , benzyl group, C ３ ~C ８ Unsubstituted cyclic alkyl groups, halogen-substituted C ３ ~C ８ Cyclic alkyl groups, C substituted with amino groups ３ ~C ８ Cyclic alkyl group, C ４ ~C ８ Unsubstituted aromatic groups, halogen-substituted C ４ ~C ８ C substituted with aromatic groups and amino groups ４ ~C ８ aromatic group, C ３ ~C １０ Heterocyclic groups, unsubstituted linear carbon chains ２ ~C １０ Alkenyl group, unsubstituted branched carbon ３ ~C １０ Alkenyl group, unsubstituted linear C ２ ~C １０ Alkynyl group and unsubstituted branched C ４ ~C １０ Individually selected from the group consisting of alkynyl groups; (B)(i)R ｂ（ｉ） ≠R ｂ（ｉｉ） (ii)R ｂ（ｉ） and R ｂ（ｉｉ） H; unsubstituted linear C １ ~C １０ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituted linear carbon group (C) substituted with one or more of the following: C, halogen, or -C(=O)H group １ ~C １０ Alkyl alkyl group; unsubstituted branched C ３ ~C １０ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched carbon (C) substituted with one or more of the following: a group, halogen, or -C(=O)H group. ３ ~C １０ Alkyl alkyl group; C ３ ~C ８ Unsubstituted cyclic alkyl groups; linear C ２ ~C １０ Alkenyl group; branched C ３ ~C １０ Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; 【Transformation 69】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Transformation 70】 Base (where n = 1 to 4 in the formula), 【Chemistry 71】 Base (where n = 1 to 4 in the formula); 【Chemistry 72】 Base (where n = 1 to 6 in the formula); 【Transformation 73】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 74】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 75】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ It is an alkylene group; and A mixture of tin clusters containing two or more tin clusters such that (c) (i) x and y are each independently equal to an integer or fraction such that 0 < x and / or y < 6, or (ii) one of x or y is 0 and the other of x or y is an integer or fraction such that 0 < x and / or y < 6.

33. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of these is an unsubstituted linear C １ ~C ４ Alkyl alkyl, unsubstituted branched C ３ ~C ４ Alkyl alkyl groups, unsubstituted linear C chains ２ ~C ６ Alkenyl group, unsubstituted branched carbon ３ ~C ６ Alkenyl group and C ４ ~C ６ The tin cluster according to claim 32, individually selected from the group consisting of unsubstituted aromatic groups.

34. (A) R ａ（ｉ） and R ａ（ｉｉ） each of which is selected individually from the group consisting of a —CH ３ group, a —CH(CH ３ ) ２ group, a —C(CH ３ ) ３ group, a —CH═CH ２ group, a —CH ２ CH═CH ２ group, a —CH ２ CH ２ CH═CH ２ group, a —CH ２ CH ２ CH ２ CH ３ group, a —C ６ H ５ group, and a —CH ２ —C ６ H ５ group: the tin cluster according to claim 32.

35. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of them is -CH ３ Base, -CH(CH ３ ) ２ Base, -CH=CH ２ The base, and -CH ２ CH ２ CH ２ CH ３ A tin cluster according to claim 32, individually selected from a group consisting of groups.

36. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them, -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituted linear carbon group (C) substituted with one or more of the following: C, halogen, or -C(=O)H group １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OH group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched carbon (C) substituted with one or more of the following: a group, halogen, or -C(=O)H group. ３ ~C ６ Alkyl alkyl group; C ３ ~C ６ Unsubstituted cyclic alkyl groups; linear C ２ ~C ６ Alkenyl group; branched C ３ ~C ６ Alkenyl group, 5-membered heterocycle, and 6-membered heterocycle; 【Transformation 76】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemical 77】 Base (where n = 1 to 4 in the formula), 【Transformation 78】 Base (where n = 1 to 4 in the formula); 【Transformation 79】 Base (where n = 1 to 6 in the formula); 【Chemistry 80】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 81】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemistry 82】 Group (where (i) n = 3 to 5, and (ii) each R ｒ is, independently, an unsubstituted methylene group, or a methylene group substituted with one or two C １ to C ４ alkyl groups); independently selected from the group consisting of; wherein R in each of the above groups ｃ is (i) a direct covalent bond, or (ii) an unsubstituted linear C １ to C ６ alkylene group, an unsubstituted branched C ３ to C ６ alkylene group, the tin cluster according to claim 32.

37. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (It is an alkyl group), -NO ２ Substituting linear carbon chains with one or more of the following groups: a group or a -C(=O)H group. １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OR' group, -SR' group, or -S-S-R' group (wherein R' is a linear or branched C) １ ~C ４ (An alkyl group), -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ (Alkyl unit), -NO ２ Substitutive branched C12C ３ ~C ６ Alkyl group; linear C chain ２ ~C ６ Alkenyl group; branched C ３ ~C ６ Alkenyl group, 【Chemistry 83】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemical 84】 Base (where n = 1 to 4 in the formula); 【Chemical 85】 Base (where n = 1 to 6 in the formula); 【Chemical 86】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 87】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemical 88】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 32, wherein the group is an alkylene group.

38. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, -OR' group (wherein R' is a linear or branched C) １ ~C ４ (which is an alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ A substituted linear C molecule (which is an alkyl group) １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, -OR' group (wherein R' is a linear or branched C) １ ~C ４ (which is an alkyl group), or -C(=O)OR'' group (wherein R'' is a linear or branched C) １ ~C ４ Substitutive branched C (which is an alkyl unit) ３ ~C ６ alkyl group; 【Chemical 89】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 90】 Base (where n = 1 to 4 in the formula); 【Chemistry 91】 Base (where n = 1 to 6 in the formula); 【Chemistry 92】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chemistry 93】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chemical 94】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 32, wherein the group is an alkylene group.

39. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of these is -H; unsubstituted linear C １ ~C ６ Alkyl group; -CN group, or -OR' group (wherein R' is a linear or branched C) １ ~C ４ A substituted linear C molecule (which is an alkyl group) １ ~C ６ Alkyl alkyl group; unsubstituted branched C ３ ~C ６ Alkyl group; -CN group, or -OR' group (wherein R' is a linear or branched C) １ ~C ４ Substitutive branched C (which is an alkyl group) ３ ~C ６ alkyl group; 【Chemical 95】 Base (wherein (i) n = 1 to 5, and (ii) each R ｒ Each of these is an unsubstituted methylene group or one or two carbon atoms. １ ~C ４ (A methylene group substituted with an alkyl group); 【Chemistry 96】 Base (where n = 1 to 6 in the formula); 【Chemistry 97】 Base (wherein each X is individually selected from O and S, and n = 1 to 4); 【Chem.98】 group (wherein each R ｍ The group is H or linear C. １ ~C ４ Chain or branch C ３ ~C ４ (Selected independently of the chain); 【Chem.99】 Base (wherein (i) n = 3 to 5, and (ii) each R ｒ These are, individually, an unsubstituted methylene group, or one or two carbon atoms. １ ~C ４ R in each of the above groups is individually selected from the group consisting of (a methylene group substituted with an alkyl group); ｃ (i) Direct covalent bond, or (ii) Unsubstituted linear C １ ~C ６ Alkylene group, unsubstituted branched carbon ３ ~C ６ The tin cluster according to claim 32, wherein the group is an alkylene group.

40. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them is -H, 【Chemistry 100】 A tin cluster according to claim 32, individually selected from the group consisting of the following.

41. (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them is -H, 【Chemistry 101】 A tin cluster according to claim 32, individually selected from the group consisting of the following.

42. (A)R ａ（ｉ） and R ａ（ｉｉ） Each of them is -CH ３ Base, -CH(CH ３ ) ２ Base, -CH=CH ２ The base, and -CH ２ CH ２ CH ２ CH ３ Individually selected from a group consisting of groups, (B)R ｂ（ｉ） and R ｂ（ｉｉ） Each of them is -H, 【Chemical Engineering 102】 A tin cluster according to claim 32, individually selected from the group consisting of the following.

43. (i) One or more Sn6-oxoclusters according to any one of claims 1 to 42, (ii) A spin-coatable formulation comprising one or more solvents suitable for use in a spin-coating process.

44. The spin-coatable formulation according to claim 43, wherein the one or more solvents suitable for use in a spin-coating process comprises one or more of alcohols, esters, ketones, lactones, diketones, solvents having an aromatic moiety, solvents having a carboxylic acid, amides, and mixtures thereof.

45. The one or more solvents suitable for use in the spin coating process include 1-methoxy-2-propanyl acetate (PGMEA), 1-methoxy-2-propanol (PGME), butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxypropanoate, methyl-3-ethoxypropanoate, methyl-3-methoxypropanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether, and ethylene glycol A spin-coatable formulation according to claim 43, comprising one or more of the following: monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, cyclopentyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, toluene, 2-heptanone, 1-hexanol, 4-methyl-2-pentanol, and anisole.

46. The spin-coatable formulation according to claim 43, wherein the one or more solvents suitable for use in a spin-coating process comprises one or more of toluene, THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol.

47. The spin-coatable formulation according to claim 43, wherein the one or more solvents suitable for use in a spin-coating process comprises one or more of THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone, and 4-methyl-2-pentanol.

48. A spin-coatable formulation according to claim 43, which does not contain toluene.

49. A spin-coatable formulation according to claim 43, comprising one of 2-heptanone, cyclohexanone, PGMEA, PGME, a mixture of anisole and PGMEA, a mixture of anisole and cyclohexanone, and a mixture of anisole and 2-heptanone.

50. The spin-coatable formulation according to claim 43, having an Sn cluster concentration of approximately 1 mg / mL to approximately 1000 mg / mL.

51. The spin-coatable formulation according to claim 43, having an Sn cluster concentration of approximately 1 mg / mL to approximately 100 mg / mL.

52. The spin-coatable formulation according to claim 43, having an Sn cluster concentration of approximately 1 mg / mL to approximately 50 mg / mL.

53. The spin-coatable formulation according to claim 43, having an Sn cluster concentration of approximately 10 mg / mL to approximately 50 mg / mL.

54. The spin-coatable formulation according to claim 43, having an Sn cluster concentration of approximately 25 mg / mL to approximately 50 mg / mL.

55. The spin-coatable formulation according to claim 43, having an Sn cluster concentration of approximately 50 mg / mL to approximately 100 mg / mL.

56. Use in an EUV process of the tin cluster according to any one of claims 1 to 42 or the spin-coatable formulation according to any one of claims 43 to 55.

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