Metal organic chalcogenolates with topological engineering, devices thereof and methods of making

Abstract

A metal organic chalcogenolate polymer is provided. The MOCha polymer has formula I: [M- E-R]∞ (I), where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho- (C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6- dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkane. Compositions, methods and devices are also provided, including methods for producing qubit(s) by delivering a spatial array of pulses to create entangled polaritons / excitons in a metal organic chalcogenolate polymer.

Description

Attorney Docket: 98121.00385 (24-023) METAL ORGANIC CHALCOGENOLATES WITH TOPOLOGICAL ENGINEERING, DEVICES THEREOF AND METHODS OF MAKING CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application is a non-provisional of and claims the benefit of U.S. Provisional Application No.63 / 585,385, filed on September 26, 2023. The entire contents of the provisional patent application is incorporated herein by reference. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under grant DE-SC0022215 awarded by the US Department of Energy Integrated Computational and Data Infrastructure for Scientific Discovery. The government has certain rights in the invention. BACKGROUND OF THE INVENTION

[0003] The present disclosure relates to quantum, photovoltaic and semiconductor materials, and in particular to metal-organic chalcogenolates.

[0004] Due to the low solar conversion efficiency of crystalline and amorphous silicon photovoltaic cells, two-dimensional materials are being explored as alternative routes to construct solar cells. Currently, the key two-dimensional materials of interest are graphene, perovskites, and transition metal dichalcogenides (TMDs). These same materials are being considered for future use as semiconductors.

[0005] Despite the promising optoelectronic properties of a variety of two-dimensional materials mentioned, there are still various drawbacks that prevent them from replacing silicon as the primary component of photovoltaic cell. Graphene has limited applications as a semiconductor and photovoltaic cell due to its lack of a band gap. Perovskites often lack long term thermal and photostability, breaking down quickly in the presence of heat, moisture, and snow. Additionally, synthesis of a large area perovskite film can be difficult to achieve. Transition metal dichalcogenides are often sensitive to substrates and their environments. Additionally, TMDs display different optoelectronic properties dependent on the number of layers of the material (for example: MoS2 is luminescent as a monolayer, but not in a bulk form). Page 1 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0006] What are needed are improved quantum materials with long-lived excitonic states and improved optoelectronic properties. SUMMARY OF THE INVENTION

[0007] This disclosure introduces a transformative approach in the fields of photovoltaic technology and semiconducting materials. Metal organic chalcogenolates (MOChas) are a new class of materials. The MOChas are air stable hybrid semiconducting materials with ligand linked optical properties.

[0008] In one aspect, metal organic chalcogenolate (MOCha) polymers are provided. The MOCha polymers have formula I: [M-E-R]∞ (I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

[0009] In another aspect, a device includes a metal organic chalcogenolate having formula I: [M-E-R]∞ (I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: -(C6H4)-OCH3, -(C6H4)-OCH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

[0010] In another aspect, a method for preparing a crystalline metal organic chalcogenolate (MOCha) is provided provided. The method includes reacting a metal precursor and a chalcogenide with a solvent. The chalcogenide including a chalcogen precursor and an organic ligand. The chalcogen precursor selected from S, Se and Te and the organic ligand selected from ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl. Page 2 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0011] In another aspect, a method for preparing metal organic chalcogenolate (MOCha) polymers having a 2-dimensional crystalline topology (2-D MOCha) is provided. The method includes reacting a metal organic chalcogenolate having a 1-dimensional crystalline topology and a chalcogenide with a displacement solvent. The chalcogenide including a chalcogen precursor and an organic ligand. The chalcogen precursor selected from S, Se and Te and the organic ligand is selected from an aryl group or an n-alkyl group.

[0012] In another aspect, a composition is provided. The composition includes a metal organic chalcogenolate polymer having formula I: [M-E-R]∞ (I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl,, a carbohydrate group, and a secondary alkyl.

[0013] The inve ntors have discovered an advanced class of metal-organic chalcogenolates offering unparalleled optical properties and stability, revolutionizing quantum materials for solar energy, semiconductor industries and quantum computing.

[0014] Systems and methods are provided for fabrication of qubit arrays, single qubit gates and multiple qubit gates from metal-organic chalcogenolates. A spatial array of pulses may be used to create entangled polaritons / excitons in metal-organic chalcogenolate materials. The systems may include a laser system, a spatial light modulator, a cryogenically cooled chamber, and metal-organic chalcogenolate materials. The systems may include a pulse shaper, a spatial light modulator and optical parametric amplifier. Programmable quantum computers may be assembled, in whole or in part, from the qubits formed from the metal-organic chalcogenolate material(s). By using an all optical approach to qubit generation, hardware complexity is reduced and scalability is facilitated. Assembly of programmable computers from metal- organic chalcogenolate material(s) using the optical approach permits on-demand production of a multitude of quantum computing configurations. Page 3 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The features and advantages of the invention are apparent from the following description taken in conjunction with the accompanying drawings in which:

[0016] FIG. 1 is a series of micrographs depicting morphologies of the materials disclosed herein;

[0017] FIG.2 is a graphic depicting x-ray diffraction patterns for embodiments of the materials disclosed herein;

[0018] FIG. 3A-3F are graphics depicting crystal structure for embodiments of the materials disclosed herein;

[0019] FIG. 4A-4C is a graphic depicting samples of embodiments of the materials disclosed herein along with graphs of spectral response;

[0020] FIG. 5 is a schematic depiction of a system for qubit generation and an associated far field two dimensional interferogram associated therewith;

[0021] FIG.6 is a schematic depiction of an alternative system for qubit generation;

[0022] FIG.7A-7D is a graphic depicting crystal structures of the materials disclosed herein;

[0023] FIG. 8A-8H is a graphic depicting crystal structures and graphs of X-ray Diffraction patterns for materials disclosed herein;

[0024] FIG.9 is a graphic depicting pXRD patterns for materials disclosed herein; and

[0025] FIG. 10 is a graphic depicting scanning electron microscope images of materials disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0026] Disclosed herein are embodiments of Metal-Organic Chalcogenolate (MOCha) polymers. MOCha polymers are a new class of nanomaterials with a unique class of hybrid organic-inorganic Van der Waals crystals in which organic ligands scaffold low-dimensional transition-metal chalcogenide inorganic structures. The MOCha hybrid assemblies contain Page 4 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) repeatable inorganic nanostructures having one- or two- dimensional (1-D, 2-D) crystalline topologies that are electronically isolated by the associated organic ligand framework.

[0027] Unlike current materials such as graphene, perovskites, and transition metal dichalcogenides, which face issues like lack of a band gap, thermal instability, and variable optoelectronic properties, MOCha polymers maintain consistent optoelectronic properties in both isolated and bulk forms. MOChas are stable up to 160°C or higher, insoluble in water, and can be synthesized in bulk.

[0028] In one aspect, metal organic chalcogenolate (MOCha) polymers are provided. The MOCha polymers have formula I: [M-E-R]∞ (I)

[0029] where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho- (C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6- dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.Metal-organic chalcogenolates (MOChas) are inorganic polymers having crystalline arrays of semiconducting 1- and 2-dimensional (1D, 2D) nanostructured wires or sheets suspended in a layer of organic ligands. The metal in the MOCha polymer may be a coinage metal. In one embodiment, the metal is Cu, Ag or Au. The MOCha polymer includes a chalcogen. In one embodiment, the chalcogen may be S, Se or Te. In one embodiment, the MOCha polymer is a silver-sulfur based MOCha polymer. In another embodiment, the MOCha polymer is a silver-selenium or a silver-tellurium based MOCha polymer. In another embodiment, the MOCha polymer is a copper-sulfur based MOCha polymer.

[0030] The MOCha polymer includes an organic ligand. Ligand design offers control for the engineering of the electronic energy landscape of the MOCha class of materials. Molecular ligand design is used to enforce inorganic topology of the inorganic polymer ensemble. In one embodiment, the organic ligand is selected from: ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary or branched alkane.In one embodiment, the MOCha polymer is silver (I) 2-methoxybenzenethiolate (AgS-Ph-ortho- OMe), silver 2-methoxybenzeneselenolate (AgSe-Ph-ortho-OMe), silver 2- Page 5 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) methoxybenzenetellurolate (AgTe-Ph-ortho-OMe), copper 2-methoxybenzenethiolate (CuS- Ph- ortho-OMe), silver (I) 3-methoxybenzenethiolate (AgS-Ph-meta-OMe), silver 3- methoxybenzeneselenolate (AgSe-Ph-meta-OMe), silver 3-methoxybenzenetellurolate (AgTe- Ph-meta-OMe), copper 3-methoxybenzenethiolate (CuS-Ph-meta-OMe), silver (I) 3-methyl mercaptobenzoate (AgS-Ph-meta-COOMe), silver (I) 4-methyl mercaptobenzoate (AgS-Ph- para-COOMe), silver 2-chlorobenzenethiolate (AgS-Ph-ortho-Cl), silver 2- bromobenzenethiolate (AgS-Ph-ortho-Br), silver terphenylthiolate (AgS-Ph3), silver 2,6- dimethylbenzenethiolate, silver cycloalkyl thiolates, silver (I) carbohydrate-thiolates or silver MOChas with secondary alkyl thiolate ligands.

[0031] In one embodiment, the silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0032] In another embodiment, the silver (I) carbohydrate-thiolates may be a silver (I) monosaccharide thiolate polymer. In one embodiment, the monosaccharide has formula - (CH2O)nwhere n is 3 or more. In another embodiment, the silver (I) carbohydrate-thiolate may be a silver (I) 1-β-D-glucose thiolate (glucose MOCha) or a silver (I) 1-β-D-galactose thiolate (galactose MOCha).

[0033] In another embodiment, the organic ligand includes a secondary or branched alkane having formula (CnH2n+1) where n is 3 or more. MOCha polymers with a secondary alkane may be silver 2-propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3- hexanethiolate, or silver 4-heptanethiolate.

[0034] The inventors found that MOCha materials exhibit an unexpected increase in optical properties as dimensionality decreases. The three archetypes of silver MOChas contain variable chalcogen atoms: mithrene (AgSePh), thiorene (AgSPh), and tethrene (AgTePh). Ligand design offers control for the engineering of the electronic energy landscape of the MOCha class of materials by the functionalization and reconfiguration of the phenyl organic ligand existing in mithrene, tethrene and thiorene.

[0035] The inventors discovered that the dimensionality of MOChas could intentionally be altered by varying the organic group and by adjusting the size and position of the functional group and that topological engineering of MOCha crystals could be used to control the dimensionality of the MOCha crystals from 2D to 1D to enhance optical emission. In some Page 6 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) embodiments, the ligand shape and design can be tailored to determine the dimensionality of the MOCha polymer product. In some embodiments, the ligand is based on an aryl ring. Increasing steric bulk at the 2 and 3 positions tends to drive the system to a 1D structure, whereas in the 4 position the system tends to adopt 2D polymers in silver. In copper, all aryl examples result in the 1D system. In some embodiments, the use of secondary carbons as the position for a chalcogen atom can drive the system towards 1D structures.

[0036] The inventors prepared silver-sulfur based MOChas by crystal functionalization of thiorene with a methoxy group at the 2- and 3- positions. Silver (I) 4-methoxybenzenethiolate (4M) has a 2-dimensional crystallinity, but the inventors surprisingly discovered that silver (I) 2-methoxybenzenethiolate (2M) and silver (I) 3-methoxybenzenethiolate (3M) have a 1- dimensional crystallinity.

[0037] FIG.1 depicts examples of morphologies of 2-D (top row) versus 1-D (bottom row) of silver organothiolates. 4M is an example of a 2-D MOCha with flat rhomboid or circular morphologies.2M and 3M are 1D MOCHas with rod-like morphologies. Flat microcrystals are obtained for silver 4-methoxybenzenethiolate (4M). Silver 2-methoxybenzethiolate (2M) and silver 3-methoxybenzenethiolate (3M) form rod-like microcrystals.

[0038] Increasing steric hindrance such as by ligand shape or by functionalization of the 2- and 3- positions around the aryl chalcogenols can reduce the dimensionality of the inorganic backbones from planar, 2-D topologies to 1-D. Generally, one-dimensional (1-D) MOChas have strength in optics and possess high emissive profiles in the UV-Vis range.

[0039] In one aspect, a metal organic chalcogenolate (MOCha) polymer having a one- dimensional crystalline structure (1-D) topology is provided. The 1-D MOCha has formula I: [M-E-R]∞(I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, 2,6-dimethylphenyl, chloro-phenyl, bromo- phenyl, a cycloalkyl, a carbohydrate group and a secondary alkyl.The metal in the 1-D MOCha polymer may be a coinage metal. In one embodiment, the metal is Cu, Ag or Au. The 1-D MOCha polymer includes a chalcogen. In one embodiment, the chalcogen may be S, Se or Te. In one embodiment, the 1-D MOCha polymer is a 1-D silver-sulfur based MOCha polymer. In Page 7 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) another embodiment, the MOCha polymer is a silver-selenium or a silver-tellurium based MOCha polymer. In another embodiment, the MOCha polymer is a copper-sulfur based MOCha polymer.

[0040] The 1-D MOCha polymer includes an organic ligand. In one embodiment, the organic ligand is selected from: ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, 2,6- dimethylphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, carbohydrates and secondary or branched alkanes.

[0041] In one embodiment, the 1-D MOCha polymer is silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver 2- chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6-dimethylbenzenethiolate, silver cycloalkyl thiolates, silver MOChas with secondary alkyl thiolate ligands or silver (I) carbohydrate-thiolates.

[0042] In one embodiment, the silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0043] In one embodiment, the silver (I) carbohydrate-thiolates may be a silver (I) monosaccharide thiolate polymer. In one embodiment, the monosaccharide has formula - (CH2O)n where n is 3 or more. In another embodiment, the silver (I) carbohydrate-thiolate may be a silver (I) 1-β-D-glucose thiolate (glucose MOCha) or a silver (I) 1-β-D-galactose thiolate (galactose MOCha).

[0044] In one embodiment, bio-MOCha polymers include carbohydrate-thiolate ligands. Bio- MOCha polymers are bigger molecules and have a higher thermal stability. The stereochemistry of these biological ligands induces chiral inorganic structures, which can provide circularly polarized luminescence (CPL), which is the emission of light with preferential left- or right-circular polarization (optical asymmetry). In one embodiment, the bio-MOCha polymers are silver glucose MOCha polymers or silver galactose MOCha polymers. These epimers form unique one-dimensional MOCha structures with strong blue and green luminescence, respectively. Moreover, the inventors discovered that hydration in the bio- Page 8 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) MOCha polymers affects the optical properties, such that uptake or release of water can cause structural distortion and subsequent change in emission.

[0045] In another embodiment, 1-D MOCha polymers include an organic ligand including a branched alkane. The incorporation of branched chain alkanethiol ligands into the MOCha polymer introduces steric hindrance and forms one-dimensional crystalline structures. MOCha polymers with secondary branched alkanes have very low melt temperatures and the potential for fluorescent properties.

[0046] In one embodiment, the organic ligand includes a secondary alkane having formula (CnH2n+1) where n is 3 or more. Examples of MOCha polymers with a secondary alkane include, but are not limited to: silver 2-propanethiolate, silver 2-butanethiolate, silver 2- pentanethiolate, silver 3-pentanethiolate, silver 3-hexanethiolate, or silver 4-heptanethiolate.

[0047] In some embodiments, 1-D MOCha polymers have fluorescent emissions that may be blue (from about 450 nm to about 500 nm), green (from about 500 nm to about 560 nm), yellow (from about 560 nm to about 590 nm) orange (from about 590 nm to about 620 nm) or red (from about 620 nm to about 750 nm). Examples of blue-emitting 1-D MOCha polymers include silver cyclohexyl thiolate (emission peak at about 500 nm) and glucose MOCha (emission peak at about 484 nm). Examples of green-emitting 1-D MOCha polymers include galactose MOCha (emission peak at about 507 nm), silver cyclopentyl thiolate (emission peak at about 512 nm), silver cyclobutyl thiolate (emission peak at about 527), silver 2- propanethiolate, (emission peak at about 534 nm), silver 2-butanethiolate (emission peak at about 537 nm), silver 3-pentanethiolate (emission peak at about 542 nm), silver 4- heptanethiolate (emission peak at about 542 nm), silver 2-bromobenzenethiolate (emission peak at about 543) and silver 3-hexanethiolate (emission peak at about 545). Examples of yellow-emitting 1-D MOCha polymers include silver (I) 2-methoxybenzenethiolate (yellow- green emission peak at about 555 nm), silver 2-chlorobenzenethiolate (emission peak at about 561 nm), silver 2-thiosalicylate (emission peak at about 579 nm), silver (I) 3- methoxybenzenethiolate (emission peak at about 587 nm), and silver cyclopropyl thiolate (emission peak at about 587 nm), Examples of orange-emitting 1-D MOCha polymers include silver 1-napthylthiolate (emission peak at about 600 nm) and silver 1-napthylselenolate. Examples of red-emitting 1-D MOCha polymers include copper 3-methoxybenzenethiolate (emission peak at about 635 nm), copper 4-methoxybenzenethiolate (emission peak at about Page 9 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) 643 nm), silver 3-methoxybenzeneselenolate (emission peak at about 644 nm), silver 2,6- dimethylbenzenethiolate (emission peak at about 680 nm), and silver 2- methoxybenzenetellurolate (emission peak at about 705 nm).

[0048] The inventors discovered that MOCha polymers with branched alkanes could provide a high optical contrast in the order-disorder transition where the melt temperature of the MOCha polymer was less than the decomposition of the MOCha polymer. In some embodiments, the MOCha polymer with branched alkane ligands has luminescent properties in the solid phase and is non-luminescent when the polymer is heated to the melting point temperature. In some embodiments, the MOCha polymers are reversible and will become luminescent again in the solid phase.

[0049] In one exemplary embodiment, silver 2-pentanethiolate exhibits non-luminescence compared to the ordered yellow-luminescent solid MOCha polymer. At room temperature, a suspension of silver 2-pentanethiolate (2-C5) in a solvent, such as isopropanol, emits yellow luminescence under 365 nm irradiation. When the 2-C5suspension is heated to melting at 60°C and the suspension is transformed into a solution state, the fluorescence is quenched. Notably, 2-C5exhibits a high optical contrast between its two liquid-solid phases, particularly during the liquid−crystal transition, a distinctive color change from yellow to absence of luminescence occurs.

[0050] MOCha materials are layered crystalline hybrid organic-inorganic materials that form through the self-assembly of metal ions and organic ligands. Ligand design enables precise control over quantum, chemical and geometric material properties (e.g., the spacing between inorganic layers). The MOCha materials may have one-dimensional or two-dimensional crystalline topologies and can exhibit quantum properties, such as emissive or excitonic states. MOCha materials can support a high density of excitons with long lifetimes enabling high coherence quantum entanglement in inexpensive substrates. Optically driven MOCha materials can generate two levels of excitons in high density and form qubits.

[0051] In an embodiment, a spatial array of pulses may be used to create entangled polaritons / excitons in MOCha materials. Each focal point of the pulse array may generate a condensate which functions as a qubit. Qubit operations are managed / leveraged through phase and amplitude control of each local condensate. Entanglement control may be achieved through control of polariton-polariton interaction which, in turn, may be controlled by the separation Page 10 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) between the spatial focal points. The array of optical foci may be generated using a spatial light modulator (SLM) with an intertwined, randomly distributed phase mask and a focusing element.

[0052] A programmable quantum computer may be assembled, in whole or in part, from the qubits formed from the MOCha material(s). By using an all optical approach, hardware complexity is reduced and scalability can be achieved, e.g., by synthesizing larger MOCha compounds and / or using larger spatial light modulators. Scalable quantum computers fabricated from MOCha compounds may operate at elevated temperatures, e.g., greater than 77oK, which expands potential applicability and utility of quantum computing systems. Assembly of programmable computers from MOCha material(s) facilitates on-demand quantum computing configurations.

[0053] A system for fabrication of entangled polaritons / excitons in MOCha materials may include a laser system, a spatial light modulator, a cryogenically cooled chamber, and MOCha materials. The MOCha materials exhibit strong coupling to light in the formation of excitons and provide strong exciton coupling through two photon transitions.

[0054] In an embodiment, the energy level and pulse duration is selected based on the MOCha material that is being processed. The laser system may provide energy per pulse on the order of ~50 µJ of energy with a repetition rate that ranges, for example, from 1 kHz to hundreds of kHz. The pulse duration may vary, e.g., based on the MOCha material being processed, and may be for example from sub-20fs to sub-200fs. The pulses may be split into two beam paths, one beam path being directed to a spatial light modulator and the other beam path being used to probe the state of the MOCha material.

[0055] The spatial light modulator (SLM) is generally selected to include a large number of pixels, include temperature management functionality and low phase ripple. A cryostat is generally provided with optical access, e.g., a chamber with an optically accessible port for optical pumping.

[0056] With reference to Fig.5, a system for qubit generation from MOCha materials is schematically depicted. Fig.5 also includes a far field two dimensional interferogram associated therewith. Page 11 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0057] As shown in Fig. 5, an array of optical pulses are delivered to a MOCha material to create an array of interacting polaritons / excitons that define qubits. The process may be controlled by programing a distribution of intensities and phases {Ai,φi} in the optical array. Calculation(s) may occur in time through the evolution of the optical pulse delivery. A time τ after a first optical array delivery, a second optical array arrives at the material and reads the state of the system through second harmonic generation.

[0058] The polariton-polariton interaction is described by the Hamiltonian, ^= Δ a^^a^ + α a^^a^^a^a^ + ^^^^∗a^^ + ^^^^a^with Δ a detuning andengineering of quantumgates may be achieved by controlling the light "pump" ^^^^ = ^e^^. This Hamiltonian canbe used to generate SWAP and sSWAP qubit gate operations. The relevance of an sSWAP operation is that it is universal. That is, any quantum operation can be represented as a combination of sSWAP gates.

[0059] Additionally, universal quantum gates may be created by using the exciton-exciton interaction, without the need of condensates. Thus, an interacting Hamiltonian is sufficient without the complexity of interacting polariton condensates. An interacting Hamiltonian is needed and then it is possible to obtain the unitary transformations for the different quantum gates,Page 12 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0060] The interaction between excitons may be controlled in two respects, e.g., through control of the distance between the two excitons by controlling the irrational slopes and through control of the relative phase between the two excitons which, in turn, is controlled by the relative phase between the multiple optical foci.

[0061] In an embodiment, a pulse shaper, a spatial light modulator and an optical parametric amplifier may be used to generate qubit arrays, single qubit gates and multiple qubit gates. The qubits may be used to build a scalable, completely programmable quantum computer. The optical pulses interact with a material that exhibits strong exciton-light coupling, e.g., a MOCha material. By using an all optical approach, hardware complexity is removed. The spatial light modulator is readily scalable and only moderately low temperatures are required. The geometry of the device is determined based on delivery of optical array, thereby permitting complete (or partial) rewiring of the device / platform “on demand”.

[0062] With reference to Fig. 6, a schematic depiction of a system for qubit generation is provided. The system includes a laser system, a spatial light modulator, an optical parametric amplifier, a pulse shaper, a cryogenically cooled chamber, and a sample that has strong exciton- light interaction, e.g., a MOCha material.

[0063] As with the embodiment described with reference to Fig. 5, the laser system may provide energy per pulse of ~100 µJ of energy with a repetition rate from 1 kHz to hundreds of kHz. Pulse duration can be from sub-20fs to sub-200fs. The pulses may be directed through an optical parametric process, e.g., an optical parametric amplifier, to create two pulses of different center wavelengths. After the optical parametric amplifier, a pulse of a first wavelength, e.g., an 800nm light pulse, may be directed to a pulse shaper, such as an acousto- optic based 4f pulse shaper. The pulse shaper may generate shaped pulses that control the amplitudes in the excitonic states. For example, for mithrene, after two photon absorptions, there are two exciton peaks corresponding to the A and B series that exhibit p-like symmetry. The relative amplitudes of the excitonic states can be controlled following the two-photon Hamiltonian:Page 13 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) where Δ=2ω_0-ω_eg is the two-photon atom-field detuning and ω_g^((s) ) (t) and ω_e^((s) ) (t) represent the time-varying dynamic Stark shifts of the ground and excited states, respectively. Control of the qubit state may be achieved by controlling the laser phase φ(t). In the perturbative limit, the Stark effect is negligible and thus, ω_(g,e)^((s) ) (t)=0. In this case, an effective Hamiltonian can be used to generate single qubit gates.

[0064] In an embodiment, the spatial light modulator includes a large number of pixels, cooling management functionality and low phase ripple. The spatial light modulator may be used to generate a spatial array of optical pulses which each generates an exciton (qubit). Interaction between qubits may be controlled by the relative phase, amplitude and distance between spatial foci, as shown in Fig. 5. Exciton-exciton interaction is equivalent to qubit-qubit interaction with interaction potential Vij through which two-qubit quantum gates can be designed.

[0065] A cryostat with optical access may include a chamber with an optically accessible port for optical pumping.

[0066] In an embodiment, an array of optical pulses may be used to create an array of interacting excitons in the MOCha material(s) that correspond to qubits. A distribution of intensities and phases {Ai,φi} in the optical array may be programmed to generate a desired product. A calculation may occur in time through the evolution of the interaction. A time τ later, a second optical array may arrive at the MOCha material and read the state of the system through second harmonic generation.

[0067] A programmable quantum computer may be assembled, in whole or in part, from the qubits formed from the MOCha material(s) using the system schematically depicted in Fig.6.

[0068] In another aspect, a device includes a metal organic chalcogenolate having formula I: [M-E-R]∞ (I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: -(C6H4)-OCH3, -(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

[0069] The metal in the MOCha polymer may be a coinage metal. In one embodiment, the metal is Cu, Ag or Au. The MOCha polymer includes a chalcogen. In one embodiment, the Page 14 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) chalcogen may be S, Se or Te. In one embodiment, the MOCha polymer is a silver-sulfur based MOCha polymer. In another embodiment, the MOCha polymer is a silver-selenium or a silver-tellurium based MOCha polymer. In another embodiment, the MOCha polymer is a copper-sulfur based MOCha polymer.

[0070] The MOCha polymer includes an organic ligand. Ligand design offers control for the engineering of the electronic energy landscape of the MOCha class of materials Molecular ligand design is used to enforce inorganic topology of the inorganic polymer ensemble. In one embodiment, the organic ligand is selected from: ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, para-(C6H4)-OCH3, ortho-(C6H4)-CO2CH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6- dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, cycloalkyl, carbohydrates, and secondary alkanes.

[0071] In one embodiment, the MOCha polymer may be silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 4-methoxybenzenethiolate, silver (I) 2-methyl mercaptobenzoate, silver (I) 3-methyl mercaptobenzoate, silver (I) 4-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver terphenylthiolate, silver 2,6-dimethylbenzenethiolate, silver (I) carbohydrate-thiolates or silver MOChas with secondary alkane thiolate ligands.

[0072] In one embodiment, the silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0073] In another embodiment, the silver (I) carbohydrate-thiolates may be a silver (I) monosaccharide thiolate polymer. In one embodiment, the monosaccharide has formula - (CH2O)n where n is 3 or more. In another embodiment, the silver (I) carbohydrate-thiolate may be a silver (I) 1-β-D-glucose thiolate (glucose MOCha) or a silver (I) 1-β-D-galactose thiolate (galactose MOCha).

[0074] In another embodiment, the organic ligand includes a secondary alkane having formula (CnH2n+1) where n is 3 or more. MOCha polymers with a secondary alkane may be silver 2- Page 15 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, or silver 4-heptanethiolate.

[0075] In another embodiment, a device includes a metal organic chalcogenolate (MOCha) polymer having a one-dimensional crystalline topology (1-D). The 1-D MOCha polymer may be silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2- methoxybenzenetellurolate, copper 2-methoxybenzenethiolate, silver (I) 3- methoxybenzenethiolate, silver 3-methoxybenzeneselenolate, silver 3- methoxybenzenetellurolate, copper 3-methoxybenzenethiolate, silver (I) 2-methyl mercaptobenzoate, silver (I) 3-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6-dimethylbenzenethiolate, silver cycloalkyl thiolates, silver (I) carbohydrate-thiolates or silver MOChas with secondary alkane thiolate ligands. In another embodiment, the 1-D MOCha polymer may be a silver (I) 1-β-D-glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2-propanethiolate, silver 2-butanethiolate, silver 2- pentanethiolate, silver 3-hexanethiolate, or silver 4-heptanethiolate. In another embodiment, the 1-D silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0076] In some embodiments, the device may be a semiconductor or a solar cell. In another embodiment, the device is a light-emitting diode (LED). In another embodiment, the MOCha materials may be used as hybrid organic-LED devices for display technology.

[0077] In another aspect, a method for preparing a crystalline metal organic chalcogenolate (MOCha) is provided provided. The method includes reacting a metal precursor and a chalcogenide with a solvent. The chalcogenide including a chalcogen precursor and an organic ligand. The chalcogen precursor selected from S, Se and Te and the organic ligand selected from ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

[0078] In one embodiment, the MOCha polymer has formula I: [M-E-R]∞(I) Page 16 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0079] where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho- (C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6- dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl. The metal in the MOCha polymer may be a coinage metal. In one embodiment, the metal is Cu, Ag or Au. The MOCha polymer includes a chalcogen. In one embodiment, the chalcogen may be S, Se or Te. In one embodiment, the MOCha polymer is a silver-sulfur based MOCha polymer. In another embodiment, the MOCha polymer is a silver- selenium or a silver-tellurium based MOCha polymer. In another embodiment, the MOCha polymer is a copper-sulfur based MOCha polymer.

[0080] The MOCha polymer includes an organic ligand. In one embodiment, the organic ligand is selected from: ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para- (C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, carbohydrates, and secondary or branched alkanes.

[0081] In one embodiment, the MOCha polymer is silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver (I) 4-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver terphenylthiolate, silver 2,6-dimethylbenzenethiolate, silver cycloalkyl thiolates, silver (I) carbohydrate-thiolates or silver MOChas with secondary alkane thiolate ligands.

[0082] In one embodiment, the silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0083] In another embodiment, the silver (I) carbohydrate-thiolates may be a silver (I) monosaccharide thiolate polymer. In one embodiment, the monosaccharide has formula - (CH2O)nwhere n is 3 or more. In another embodiment, the silver (I) carbohydrate-thiolate may be a silver (I) 1-β-D-glucose thiolate (glucose MOCha) or a silver (I) 1-β-D-galactose thiolate (galactose MOCha).

[0084] In another embodiment, the organic ligand includes a secondary alkane having formula (CnH2n+1) where n is 3 or more. MOCha polymers with a secondary alkane may be silver 2- Page 17 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, or silver 4-heptanethiolate.

[0085] In one embodiment, the metal precursor and a chalcogenide polymer including an organic ligand are mixed with a solvent. The metal precursor may be a metal oxide or salt. In one embodiment, the metal precursor is MpXq where M is a metal, X is an oxide or salt, p is 1 or 2 and q is 1, 2 or 3. In one embodiment, the metal is Cu, Ag or Au. In another embodiment, X is selected from O, NO3, SO4, Cl, Br, CH3CO2, CF3SO3, PF6, BF4 and ClO4. In one embodiment, the metal precursor is Ag2O.

[0086] The solvent may be any suitable solvent for dissolving the metal precursor and chalcogenide polymer in a reaction mixture. The solvent may include, but is not limited to methanol, ethanol, acetone, isopropyl alcohol, or water.

[0087] The reaction mixture may proceed at room temperature or may be heated. In one embodiment, the reaction mixture may be heated up to 90°C. In another embodiment, the reaction temperature is from about 70oC to about 90°C. In one embodiment, the reaction may proceed for up to 5 days. In another embodiment, the reaction time is from about 1 day to about 5 days. In another embodiment, the reaction time is from about 1 day to about 3 days. In another embodiment, the reaction time is from about 2 days to about 4 days.

[0088] In some embodiments, the displacement of MOChas by diorganic dichalcogenides can yield a new MOCha and an asymmetric byproduct. In one embodiment, asymmetric disulfide products were obtained from 2MMB to thiorene using diphenyl disulfide with recovered yields as high as 90%. Additionally, it was observed that the transformation of 1D MOCha to 2D thiorene via disulfide exchange is feasible without solvent. Overall, the S−S bond underwent polarization, resulting in one sulfur atom carrying a partial positive charge and the other sulfur atom exhibiting a partial negative charge. This facilitated collision with a polarized Ag−S bond, initiating a metathesis reaction. The displacement will occur favoring the most nucleophilic ligand, so this is a straightforward way to create asymmetric dichalcogenides without catalysts or purification required.

[0089] In order to generate the asymmetric dichalcogenide in high yield, the reaction can be set up to run with a substoichiometric portion of the replacing ligand. The reaction can be incubated until all of the diorganic dichalcogenide is consumed. The remaining byproduct can Page 18 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) be extracted or removed by sublimation from the mixture of the two mochas. This can be done to yield both asymmetric dichalogenides where the dichalcogenide is the same, but also asymmetric dichalcogenides having the form: RSAg + R'SSR' --> RSSR' + R'SAg or RSAg + R'SeSeR' --> RSSeR' + R'SeAg,

[0090] where RSAg is a 1-D MOCha polymer as described above, S is sulfur, Se is selanium, Ag is silver, R is an organic ligand as previously described for a 1-D MOCha polymer and R’ is an aryl or n-alkyl group.

[0091] In some embodiments the mocha byproducts can be further separated to recover the starting materials. The remaining solid product can be treated with more of the dichalcogenide to drive the reaction to completion. The solid product will thus have ligands from only the displacing class. These can be recovered by heating the sample to decomposition and recovering the organic phase and silver metal.

[0092] In one aspect, a method for preparing metal organic chalcogenolate (MOCha) polymers having a 2-dimensional crystalline topology (2-D MOCha) is provided. The method includes reacting a metal organic chalcogenolate having a 1-dimensional crystalline topology and a dichalcogenide. The dichalcogenide including a chalcogen precursor and an organic ligand. The chalcogen precursor selected from S, Se and Te and the organic ligand is selected from an aryl group or an n-alkyl group.

[0093] The 2-D MOCha has formula I: [M-E-R]∞ (I) where M is a metal; E is S, Se or Te; and R is an aryl group or an n-alkyl group.

[0094] The metal M may be a coinage metal. In one embodiment, the metal is Cu, Ag or Au. R is an aryl group or an n-alkyl group. In one embodiment, the aryl group may be a phenyl, biphenyl or a terphenyl. In another embodiment, the n-alkyl group has the formula CnH2n+1 where n is 2 or more. In another embodiment, the n-alkyl group may be ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Page 19 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0095] The metal organic chalcogenolate having a 1-dimensional topology may be any metal organic chalcogenolate have a one-dimension crystalline topology as previously described.

[0096] In one embodiment, the reaction may include a displacement solvent. The displacement solvent may be any suitable solvent for dissolving the metal organic chalcogenolate having a 1-dimensional crystalline topology and the chalcogenide in a reaction mixture. In one embodiment, the displacement solvent is N-methyl-2-pyrrolidone (NMP).

[0097] The reaction mixture may proceed at room temperature or may be heated. In one embodiment, the reaction mixture may be heated up to 90°C. In another embodiment, the reaction temperature is from about 70oC to about 90°C. In one embodiment, the reaction may proceed for up to 5 days. In another embodiment, the reaction time is from about 1 day to about 5 days. In another embodiment, the reaction time is from about 1 day to about 3 days. In another embodiment, the reaction time is from about 2 days to about 4 days.

[0098] In another aspect, a composition is provided. The composition includes a metal organic chalcogenolate polymer having formula I: [M-E-R]∞(I)

[0099] where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho- (C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6- dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.The metal in the MOCha polymer may be a coinage metal. In one embodiment, the metal is Cu, Ag or Au. The MOCha polymer includes a chalcogen. In one embodiment, the chalcogen may be S, Se or Te. In one embodiment, the MOCha polymer is a silver-sulfur based MOCha polymer. In another embodiment, the MOCha polymer is a silver- selenium or a silver-tellurium based MOCha polymer. In another embodiment, the MOCha polymer is a copper-sulfur based MOCha polymer.

[0100] The MOCha polymer includes an organic ligand. In one embodiment, the organic ligand is selected from: ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)- CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, carbohydrate groups, and secondary or branched alkanes. Page 20 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0101] In one embodiment, the MOCha polymer may be silver (I) 2- methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2- methoxybenzenetellurolate, copper 2-methoxybenzenethiolate, silver (I) 3- methoxybenzenethiolate, silver 3-methoxybenzeneselenolate, silver 3- methoxybenzenetellurolate, copper 3-methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver (I) 4-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver terphenylthiolate, silver 2,6-dimethylbenzenethiolate, silver cycloalkyl thiolates, silver (I) carbohydrate-thiolates or silver MOChas with secondary alkane thiolate ligands.

[0102] In one embodiment, the silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0103] In another embodiment, the silver (I) carbohydrate-thiolates may be a silver (I) monosaccharide thiolate polymer. In one embodiment, the monosaccharide has formula - (CH2O)nwhere n is 3 or more. In another embodiment, the silver (I) carbohydrate-thiolate may be a silver (I) 1-β-D-glucose thiolate (glucose MOCha) or a silver (I) 1-β-D-galactose thiolate (galactose MOCha).

[0104] In another embodiment, the organic ligand includes a secondary alkane having formula (CnH2n+1) where n is 3 or more. MOCha polymers with a secondary alkane may be silver 2-propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3- hexanethiolate, or silver 4-heptanethiolate.

[0105] In another embodiment, the composition includes a metal organic chalcogenolate (MOCha) polymer having a one-dimensional crystalline topology (1-D). The 1-D MOCha polymer may be silver (I) 2-methoxybenzenethiolate, silver 2- methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver 2- chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6-dimethylbenzenethiolate, silver cycloalkyl thiolates, silver (I) carbohydrate-thiolates or silver MOChas with secondary alkane thiolate ligands. In another embodiment, the 1-D MOCha polymer may be a silver (I) 1-β-D-glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2-propanethiolate, silver 2- Page 21 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, or silver 4-heptanethiolate. In another embodiment, the silver cycloalkyl thiolates may be silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate.

[0106] In some embodiments, the composition may be a coating or a film. EXAMPLES EXAMPLE 1

[0107] Synthesis of silver 2-methoxybenzenethiolate (2M), 3-methoxybenzenethiolate (3M), and 4-methoxybenzenethiolate (4M). Silver (I) oxide (>99.0%) and 2- methoxythiophenol (97%) were used as received by MilliporeSigma (St. Louis, MO). Isopropyl alcohol (ACS grade) was used as received by Lab Chem (Zelienople, PA). 100 mg of silver (I) oxide was combined with ~200 µL of 2-methoxythiophenol (two time excess) in a 1-dram vial with a chemically inert lid and placed in a furnace set at 80°C for 24 hours. Afterwards, the vial was removed and allowed to cool down for 5-10 minutes. The sample had a yellow tinge to it with black unreacted silver oxide also located in the vial.2mL of isopropyl alcohol was added to the vial and it was then vigorously shaken to uproot the sample and allow for the remaining silver oxide to react. The sample was then placed back into the furnace at 70°C for another 24-48 hours. The black silver (I) oxide precursor underwent a color change to a yellow hue for silver 2- methoxybenzenethiolate (2M). The process was repeated using 3- methoxythiophenol (two time excess) and repeated again using 4-methoxythiophenol (two time excess). The black silver (I) oxide precursor underwent a color change to a yellow hue for silver 3- methoxybenzenethiolate (3M). The black silver (I) oxide precursor underwent a color change to a white hue for silver 4- methoxybenzenethiolate (4M). A combination of centrifugation and filtration outlined below was used to isolate and dry the product.

[0108] Purification & Isolation. The sample was first transferred to a 15mL centrifuge tube with excess IPA and underwent one round of centrifugation. The solvent was decanted, and fresh solvent was used to filter the material via a UF sintered funnel. It was washed two times with IPA and a final rinse of acetone before the product was collected and stored for future characterization. The combination of the two purifying methods was used to speed up the filtration process by removing the excess ligand first, to prevent the clogging of the pores in the funnel. Page 22 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0109] To isolate and purify the product, centrifugation or filtration can be used. With centrifugation, the sample is transferred with excess IPA into a centrifuge tube. Sonication of the vial can help with the dismounting of product on the bottom of the glass vial. Sample is then centrifuged three times at 5000 rpm for 10 minutes (Sorvall ST 8 Small Benchtop Centrifuge). After each cycle, the top layer consisting of IPA and excess organochalcogenolate ligand was decanted and 20 mL of fresh IPA was added. Sample was vigorously shaken to re- suspend the nanocrystals in the fresh solvent. After decantation of the third cycle, the sample can be stored in 5 mL of IPA in the freezer for future characterization or dried to its powder form via evaporation of the IPA on a watch glass under the hood. The powdered sample is transferred into a 0.5-dram vial for storage in a freezer.

[0110] For filtration, an ultra-fine (UF) Hirsch sintered funnel is required with a pore size of 1.0– 1.6 µm given MOChas tendency to crystallize between 2-10 µm. A standard vacuum filtration is set up with the UF sintered funnel and a suspension of the MOCha crystal is filtered through. IPA is used to rinse the product up to three times. The product is lastly rinsed with acetone to aid the drying process. The powdered sample is transferred into a 0.5- dram vial for storage in a freezer. EXAMPLE 2

[0111] Synthesis of silver (I) methyl 2-mercaptobenzoate (2MMB). Silver (I) oxide (>99.0%) and methyl thiosalicylate (98%) were used as received by MilliporeSigma (St. Louis, MO) and AK Scientific (Union City, CA), respectively. Isopropyl alcohol, ACS grade was used as received by Lab Chem (Zelienople, PA). Acetone (99.6%) ACS Reagent was used as received by Thermo Scientific (Waltham, MA). For small-scale synthesis of silver methyl thiosalicylate (AgS-MTS), 100 mg of silver (I) oxide was added to a 1-dram vial with a 2.5 molar equivalent of methyl thiosalicylate and 0.5 mL of acetone. The solution was lightly swirled, sealed with a chemically inert lid, and placed in a furnace under the hood at ~80°C for five days. Once the black silver (I) oxide converted to the yellow product, the reaction was deemed complete. Centrifugation outlined above was used to isolate the product. Results for EXAMPLES 1and 2

[0112] FIG. 1 depicts examples of morphologies of 2-D (top row) versus 1-D (bottom row) of silver organothiolates.4M and 4MMB are examples of 2-D MOCha polymers with flat Page 23 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) rhomboid or circular morphologies. 2M, 3M and 2MMB are 1-D MOCHas with rod-like morphologies. All examples indicate that the MOCha polymer ability forms singular microcrystals that are an ideal match for smSFX characterization. Flat microcrystals are obtained for silver 4-methoxybenzenethiolate (4M) and silver methyl 4-mercaptobenzoate (4MMB). Aside from the step edges, the individual crystals appear largely featureless. Silver 2-methoxybenzethiolate (2M), silver 3-methoxybenzenethiolate (3M), and silver methyl 2- mercaptobenzoate (2MMB) form rod-like microcrystals.

[0113] A series of x-ray diffraction (XRD) patterns of 1D MOChas (2M, 3M, 2MMB) compared to 2D MOChas (4M, 4MMB) is shown in FIG. 2. In FIG. 2, the profiles obtained from a sample consisting of either 1D or 2D MOCha microcrystals are presented. 4MMB and 4M obtained diffraction peaks that are consistent with patterns expected for 2D MOCha systems with evenly spaced peaks of declining intensity, best observed in 4M. With 2MMB, 3M, and 2M, the diffraction peaks are no longer evenly spaced and tend to exhibit peak splitting. In the case of the silver methoxybenzethiolate series (2M, 3M, 4M), the position of the methoxy functional group affected the morphology of the crystal observed in FIG.1 where 2M and 3M have rod-like habits while 4M exists in plates. This is further seen in the pXRD data where 4M obtains a different diffraction peak pattern relative to 2M and 3M. 4MMB, similar to 4M, also exhibits plate-like morphology and has a similar diffraction peak pattern that has become familiar to 2D MOChas. Rod-like 2MMB shares similarity in its diffraction pattern with 2M and 3M.

[0114] In FIG. 3A-3F, examples of crystal structures are shown. FIG. 3A shows the crystal structure of silver 3-methoxybenzenethiolate (3M) and FIG. 3D shows the silver and sulfur network for the 3M polymer. FIG. 3B shows the crystal structure of silver 4- methoxybenzenethiolate (4M) and FIG. 3E shows the silver and sulfur network for the 4M polymer. FIG. 3C shows the crystal structure of silver methyl 2-mercaptobenzoate (2MMB) and FIG. 3F shows the silver and sulfur network for the 2MMB polymer. In these examples, 3M and 2MMB are 1-dimensional; while the 2M crystal structure was not solved, given its similarity in morphology and pXRD patterns to 3M and 2MMB, it is likely that it also consists of a 1D structure. 4M is 2D; as stated above, given the similarity of the plate-like morphology and evenly spaced peaks in its pXRD pattern, 4MMB is considered to consist of a 2D structure as well. Page 24 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0115] Photoluminescence (PL) spectroscopy has been widely used to characterize the intrinsic properties of materials; MOChas included. PL spectroscopy combined with lifetime and quantum yield measurements indicates the effect of subtle ligand changes on the structure and resulting optical phenomena. One-dimensional MOChas were optically active while the two-dimensional MOChas were not (reference blacklight luminescence image). To further investigate, the PL spectra ranging from 350 to 700nm are shown in FIG. 4B. Broad emission peaks at 555nm, 589nm, and 579nm were observed for 2M, 3M and 2MMB, respectively.

[0116] In FIG. 4A, there is shown solid-state powder samples of relatively labelled 2MMB, 2M, 3M, and 4M illuminated by a 254 nm blacklight. Images of the high luminescence in 2MMB and 3M which are conferred by the Photoluminescent Quantum Yield (PLQY), 22% and 1%, and photoluminescent lifetime measurements of 201 ns and 144 ns, respectively. FIG. 4B shows a normalized absorption spectra in the region 350 – 550 nm of five MOCha species (2M, 3M, 4M, 2MMB, 4MMB). FIG. 4C shows a normalized emission spectra in the region 450 – 680 nm of the five MOChas listed in FIG. 4B, which were suspended in ethanol and filtered through a 5 µm syringe filter to lessen scattering effects of larger suspended crystals. All species were excited at 360 nm.

[0117] With the goal of linking optoelectronic activity as a function of structure in MOChas, the emissive samples of 2M, 3M and 2MMB were further explored with 4M and 4MMB serving as the control non-emissive 2D samples. Powder solid-state absorption measurements were taken of five species of MOCha microcrystals (AgSRPh, R = OCH3 (M), COOCH3 (MMB)). The 1D MOChas (2M, 3M, and 2MMB) exhibit at least two absorption peaks. All three have one at ~415 nm and the second peak varying, but all <370 nm. The 2D MOCHas (4M, 4MMB) exhibit an absorption peak at ~360 nm.

[0118] Liquid suspension of MOCha crystals in ethanol were excited at 360nm, above the bandgap for all five species.2M, 3M and 2MMB exhibit an emission peak at 555 nm, 589 nm, and 579 nm respectively, with the 2M emission being of significantly lower intensity pre- normalization of data. As seen in FIG. 4A, 2M is not luminescent under a blacklight. The % PLQY and the lifetime measurements further indicate that it is not a highly fluorescent sample, while the emission data continues to indicate that in the silver-sulfur family of MOChas, only the 1D materials have emissive profiles.4M and 4MMB do not fluoresce in the UV-Vis range. Page 25 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0119] To quantitatively assess the fraction of photons emitted versus the number of photons absorbed by the MOChas, the photoluminescence quantum yield (PLQY) was measured on a dilute solution of the MOChas in ethanol, where the limits of PLQY are from 0 to 1, translated to percentages of 0 to 100%.2M and 4M were not found to exhibit any PLQY, while the most fluorescent MOCha in the methoxy series, 3M, was calculated to have a PLQY between 0.01-0.02. 2MMB, another 1D MOCha like 2M and 3M, also possessed strong photoluminescent properties, however there is a considerable leap in PLQY where the number jumped to the range 0.16-0.22.

[0120] It is interesting that 2M does not exhibit any PLQY given it is a 1D MOCha like 3M and 2MMB, but as noted in the emission measurements, 2M exhibited a significantly lower fluorescence intensity pre-normalization of data. This doesn’t necessarily mean that 2M doesn’t exhibit QY, given its similarity to 3M and 2MMB, but that there could be a quenching effect present due to the fact that the typical photon trajectory in a multi-layered structure can demand ~25 absorption / emission events before a single photon can escape.

[0121] For the methoxy series, the presence of strong fluorescence and PLQY can then be attributed to differences in the crystal structures of the three isomeric methoxy based MOChas. 4MMB was not found to exhibit any PLQY, once again indicating that between 2MMB and 4MMB, there is a relationship between crystal structure / dimensionality and optical properties. Unexpected Optical Properties were seen for the 2MMB.

[0122] Scanning Electron Microscopy. Samples were prepared for SEM imaging by first transferring 1-2mg of the microcrystalline powder into 2mL of Ethanol 200 Proof used as received from Deacon Labs Inc. (Prussia, PA) via disposable microspatulas. Typically, this occurred in a small 0.5-dram vial that was then sealed and underwent sonication for 10-15 minutes to break up crystal clumps. During sonication, a 5x7mm precut silicon wafer chip from Ted Pella Inc. (Redding, CA) was acquired and prepared by first cleaning it with compressed nitrogen air for 10 seconds. The wafer was placed on a flat surface and a few drops of the sonicated MOCha suspension were transferred to the clean wafer via a glass Pasteur pipette. Once all the solvent evaporated, the wafer was attached to a standard SEM pin stub mount (Ted Pella; Redding, CA) using double-coated carbon conductive tabs (Ted Pella; Redding, CA). The stub was then placed into a desiccator for further drying and storage. Page 26 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0123] Considering the tendency of these MOChas to crystallize <5µm, the samples were imaged on a Field Emission Nova Nano SEM 450 in high vacuum mode with the use of a Through the Lens Detector (TLD).

[0124] Powder X-Ray Diffraction. Dried powder MOCha samples were transferred into a zero diffraction Si plate with a cavity. The cavity was filled up with the microcrystalline powder and the surface was smoothed out with a clean glass microscope slide. XRD patterns for the samples were then collected from 5-65 two theta degrees on a Bruker D2 Phaser.

[0125] UV-Vis. Absorption data was collected on a Cary 4000 UV-Vis (Agilent; Santa Clara, CA). With the powder cell kit attachment, absorption data was collected on the solid powders with then use of a diffuse reflectance accessory (DRA) to minimize loss of absorption due to scattering.

[0126] Fluorescence. Fluorescence data was collected on a Cary Eclipse Fluorescence Spectrometer (Agilent; Santa Clara, CA). 2-3 mg of sample were suspended into 5mL of ethanol 200 Proof (Decon Labs; Prussia, PA) as received. Solutions were transferred into fluorescence quartz cuvettes for data collection. All samples were excited at 360 nm which is above the bandgap for all materials.

[0127] Quantum Yield. The quantum yield (QY) of the samples was measured using a spectrofluorometer (Fluoromax plus, HORIBA Scientific) equipped with a 152 mm diameter integrating sphere (Quanta – Phi, HORIBA Scientific). Ethanol was used for the blank measurement and the test samples were diluted in ethanol (4mg / mL) to an optical density of ≤ 0.05 at the excitation wavelength. A standard 1cm quartz fluorescence cuvette was used for all the measurements. The samples were excited at 405 nm and the emission was collected between 395 nm and 750 nm.

[0128] Time-Decay. The samples were diluted in ethanol (4mg / mL) and excited with a 405 nm pulsed diode laser (LDH-P-C-405, PicoQuant) at a 2.5 MHz repetition rate. The emitted light from the samples was filtered through a 450 nm longpass filter to measure the photoluminescence (PL) decay. The photons emitted were detected with a single photon counting detector (SPAD, PicoQuant) and recorded with a time-correlated single photon counting module (PicoHarp 300, PicoQuant) at a resolution of 64 ps. The PL decays were fitted using the commercial software FAST (Edinburgh Instruments). Page 27 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) EXAMPLE 3

[0129] Synthesis of glucose MOCha and galactose MOCha: 1-Thio-b-D-glucose sodium salt (≥98%, T6375), 1-Thio-b-D-galactose sodium salt (95%, 27793), and silver (I) nitrate (≥99.0%, 209139) were used as received from Sigma Aldrich. Microcrystalline silver(I) 1-β-D-glucosethiolate (glucose MOCHa) and silver(I) 1 -β-D-galactosethiolate (galactose MOCHa) were prepared in the same approach only needing to change the corresponding thiol ligand. Specifically, a solution of 1-Thio-b-D-glucose sodium salt (218 mg, 1 mmol) in H2O (2 mL) was added to AgNO3(85 mg, 0.5 mmol) dissolved in H2O (2 mL) in a 20 mL glass vial. Then, 4 mL methanol was added to this vial. The reaction was allowed to stir for 4 days at room temperature. A white precipitate was obtained and washed 4 times with 2 aliquots of 10 mL of H2O, and 2 aliquots with 10 mL of acetone.

[0130] Characterization: FIG. 7A shows a scanning electron micrograph (SEM) of glucose MOCha and FIG.7B shows an SEM of galactose MOCha. The SEMs in FIGs.7A and 7B revealed that both bio-MOChas consist of needle-shaped crystallites with diameters of a few hundred nanometers and lengths extending to several micrometers. The crystal structure of the resultant MOChas was characterized by small-molecule serial femtosecond X-ray crystallography (smSFX). The smSFX analysis at 298 K revealed that glucose MOCha and galactose MOCha form a hybrid organic-inorganic structure with a 1D inorganic core composed of Ag and S atoms, surrounded by organic 1-β-D-glucose and 1-β-D-galactose motifs, respectively. Fig. 7C shows the Crystal structure of hydrated glucose MOCha in a Tessellation pattern (glucose MOCha is viewed along the c axis). FIG. 7D shows the Crystal structure of hydrated galactose MOCha in a Tessellation pattern (galactose MOCha is viewed along the b axis). EXAMPLE 4

[0131] Synthesis and Properties of Branched-chain MOChas

[0132] The synthesis of five branched chain MOChas—specifically silver 2- propanethiolate (2-C3), silver 2-butanethiolate (2-C4), silver 2-pentanethiolate (2-C5), silver 3- hexanethiolate (3-C6), and silver 4-heptanethiolate (4-C7) was carried out under solvothermal conditions at 70 ̊C for 3 days. This synthesis employed commercially available secondary branched chain thiol ligands tailored to each MOCHa, in combination with Ag2O, as illustrated Page 28 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) in FIG.8A. Following synthesis, the resulting solids were isolated through centrifugation, with some achieving an excellent yield of up to 98%.

[0133] Powder X-ray Diffraction (PXRD) analysis showed the crystallinity and isostructural characteristics across all five MOChas, as evidenced by containing closely positioned double or split peaks in the low-angle dominant zone, implying a non-layered system in the silver-sulfur MOCha as shown in FIG.8E. Notably, in the case of 2-C4, a distinct observation was made with both single and split peaks, particularly at 2theta values below 10, signifying a potential phase separation within this specific MOCHa as shown in FIG.8F.

[0134] The morphological characteristics of the synthesized MOCHas were obtained through scanning electron microscope (SEM) imaging, as presented in FIGs 8B, 8C, 8D, 8G and 8H. Needle-shaped crystallites with diameters in the few hundred nanometers range and lengths extending into the micrometer scale were observed for 2-C3, 2-C4, 3-C6, and 4-C7, although 2-C5 exhibited an amorphous-like morphology attributed to its lower melting temperature, which is consistent with an expected 1D shape. EXAMPLE 5

[0135] Materials: Methyl thiosalicylate (C8H8O2S, 97%), benzenethiol (C6H6S, 97%), benzeneselenol (C6H6Se, 97%), biphenyl-4-thiol (C12H10S, 97%), 1,1′,4′,1′′-terphenyl-4-thiol (C18H14S, 97%), diphenyl diselenide (C12H10Se2, 97%), diphenyl disulfide (C12H10S2, 97%), acetone (CH3COCH3, 99.9%), and N-methyl-2-pyrrolidone (NMP, 99.0%) were used as received from Sigma Aldrich. Silver (I) oxide (Ag2O, 99%, Fisher Scientific), and isopropanol (IPA, 100%, LabChem) were used as received without further purification.

[0136] Safety note: Liquid thiol reagents are foul smelling and should be handled with care. Heating and stirring of reagents is performed in a fume hood and with heating blocks on stir plates.

[0137] Synthesis of 1D MOCha - silver (I) methyl 2-mercaptobenzoate (2MMB) and reference samples of thiorene and mithrene. Silver (I) oxide (70 mg, 0.3 mmol) and either methyl thiosalicylate (202 mg, 1.2 mmol), benzenethiol (132 mg, 1.2 mmol), or benzeneselenol (188 mg 1.2 mmol) were placed in isopropanol (2 mL). The vial was sealed and heated to 70°C in an oven or stirred at 70°C for 3 days. After cooling to room temperature, isopropanol (2 Page 29 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) mL) was added, and the suspension was sonicated for about 10 min. After centrifugation (~5,000 rpm for 5 min), the organic solvent was removed, and the powder was washed with acetone (5 mL x 1) and isopropanol (5 mL x 2). The powder collected was dried in the air for 48 h.

[0138] The transformation route for 2D thiorene, mithrene, silver (I) biphenylthiolate (AgSBP) and silver(I) terphenylthiolate (AgSTP). Thiorene, mithrene, AgSBP, and AgSTP were synthesized by mixing 14 mg (0.05 mmol) of 2MMB with the corresponding ligand, specifically 1.2 equivalent of benzenethiol, 2.0 equivalents of diphenyl disulfide, 1.2 equivalents of benzeneselenol, 2.0 equivalents of diphenyl diselenide, 1.5 equivalents of biphenyl-4-thiol, or 2.0 equivalents of 1,1′,4′,1′′-terphenyl-4-thiol in 1 mL of NMP. The vial was sealed and stirred at 90°C for 24 hours. After cooling to room temperature, 2 mL of isopropanol was added, and then each product was sonicated for 10 minutes. Each sample was centrifuged (~5,000 rpm for 5 min), and the organic solvent was decanted. The solid was then washed with 5 mL of acetone (once) and 5 mL of isopropanol (twice). The collected powder was air-dried for 48 hours.

[0139] Characterization. Powder X-ray diffraction (XRD) patterns were recorded on a Bruker D2 diffractometer with Bragg-Brentano θ-2θ geometry (30 kV and 10 mA) using a nickel filter with a Cu Kα radiation source. FIG.9 presents pXRD performed to identify phases, and these are matched to known values. In each case, no evidence of the 2MMB is found, and the mithrene and thiorene products are 1:1 matches to literature values. All of the pXRD patterns are typical of layered or 2D MOCha, with evenly spaced high intensity peaks at low angle corresponding to the dominant zone of the layered crystals. These low-angle peaks are sufficient to identify phases of known materials, although an ideal isotropic powder pattern will also reveal extensive high-angle structure. Both silver biphenylthiolate (AgSBP) and silver terphenylthiolate (AgSTP) are crystalline and similarly exhibit evenly spaced peaks, consistent with other layered MOChas.

[0140] Morphologies of the crystals were characterized using scanning electron microscopy (SEM) on a Phenom ProX Tabletop SEM at accelerating voltages of 5 or 15 kV and EDS were collected with a 15 kV accelerating voltage. Scanning electron microscopy (SEM) images are collected in FIG. 10. Panels a) and b) depict thiorene with distinct "S" ligands in the transformation process, while panels c) and d) show mithrene with different "Se" Page 30 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) ligands. Panel e) exhibits AgSBP utilizing the biphenylthiol ligand, and panel f) displays AgSTP using the terphenylthiol ligand.

[0141] Generally, as used herein “chalcogenide” as used herein refers to a compound containing a chalcogen. “Chalcogen” as used herein refers to an element of the periodic table from Group VI (ie, sulfur, selenium, tellurium). “MOCHA” as used herein, refers to a metal- organic chalcogenide assembly, and is a general material class for any crystalline assembly of hybrid coordination polymers.

[0142] In some embodiments, the resulting materials are layered. In some embodiments, such compositions are for use in a fluorescent resonance energy transfer (FRET) assay. In some embodiments, such compositions are for use as photocatalysts. In some embodiments, such compositions are for use in devices. In some embodiments, the device is a semiconductor. In some embodiments, the device is a solar cell. In some embodiments, the device is a laser. In some embodiments, the device is a light-emitting diode (LED). These components may be used, in turn, in other devices such as a display.

[0143] The materials disclosed herein may be used in conjunction with other devices, including, for example, light sources and / or amplifiers, to enhance optical effects thereof.

[0144] All statements herein reciting principles, aspects, and embodiments of the disclosure, as well as specific examples thereof, are intended to encompass both structural and functional equivalents thereof. Additionally, it is intended that such equivalents include both currently known equivalents as well as equivalents developed in the future, i.e., any elements developed that perform the same function, regardless of structure.

[0145] Various other components may be included and called upon for providing for aspects of the teachings herein. For example, additional materials, combinations of materials and / or omission of materials may be used to provide for added embodiments that are within the scope of the teachings herein. Adequacy of any particular element for practice of the teachings herein is to be judged from the perspective of a designer, manufacturer, seller, user, system operator or other similarly interested party, and such limitations are to be perceived according to the standards of the interested party. Page 31 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023)

[0146] In the disclosure hereof any element expressed as a means for performing a specified function is intended to encompass any way of performing that function including, for example, a) a combination of circuit elements and associated hardware which perform that function or b) software in any form, including, therefore, firmware, microcode or the like as set forth herein, combined with appropriate circuitry for executing that software to perform the function. Applicants thus regard any means which can provide those functionalities as equivalent to those shown herein. No functional language used in claims appended herein is to be construed as invoking 35 U.S.C. §112(f) interpretations as “means-plus-function” language unless specifically expressed as such by use of the words “means for” or “steps for” within the respective claim.

[0147] When introducing elements of the present invention or the embodiment(s) thereof, the articles “a,” “an,” and “the” are intended to mean that there are one or more of the elements. Similarly, the adjective “another,” when used to introduce an element, is intended to mean one or more elements. The terms “including” and “having” are intended to be inclusive such that there may be additional elements other than the listed elements. The term “exemplary” is not intended to be construed as a superlative example but merely one of many possible examples.

[0148] The term “about” used throughout this specification is used to describe and account for small fluctuations. For example, the term “about” can refer to less than or equal to ±5%, such as less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal less than or equal to ±0.1% or less than or equal to ±0.05%. All numeric values herein are modified by the term “about,” whether or not explicitly indicated. A value modified by the term “about” of course includes the specific value. For instance, “about 5.0” must include 5.0. Page 32 of 41ME150163641v.1

Claims

Attorney Docket: 98121.00385 (24-023) CLAIMS What is claimed is:

1. A metal organic chalcogenolate polymer having formula I: [M-E-R]∞ (I) wherein M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

2. The metal organic chalcogenolate polymer of claim 1, wherein M is Cu, Ag or Au.

3. The metal organic chalcogenolate polymer of claim 2, wherein M is Ag and E is S.

4. The metal organic chalcogenolate polymer of claim 1, wherein the polymer is selected from the group consisting of: silver (I) 2-methoxybenzenethiolate, silver 2- methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver (I) 4-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver terphenylthiolate, silver 2,6-dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, silver cyclohexyl thiolate, a silver (I) 1-β-D- glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2-propanethiolate, silver 2- butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, and silver 4-heptanethiolate.

5. The metal organic chalcogenolate polymer of claim 1, wherein the metal organic chalcogenolate polymer has a one-dimensional crystalline structure, and wherein R is an organic ligand selected from ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, 2,6-dimethylphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group and a secondary alkane.

6. The metal organic chalcogenolate polymer of claim 5, wherein M is Cu, Ag or Au. Page 33 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) 7. The metal organic chalcogenolate polymer of claim 6, wherein M is Ag and E is S.

8. The metal organic chalcogenolate polymer of claim 5, wherein the polymer is selected from the group consisting of: silver (I) 2-methoxybenzenethiolate, silver 2- methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver 2- chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6-dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, silver cyclohexyl thiolate, a silver (I) 1-β-D-glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2-propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3- hexanethiolate, and silver 4-heptanethiolate.

9. A composition comprising a metal organic chalcogenolate polymer having formula I: [M-E-R]∞(I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkane.

10. The composition of claim 9, wherein M is Cu, Ag or Au.

11. The composition of claim 10, wherein M is Ag and E is S.

12. The composition of claim 9, wherein the polymer is selected from the group consisting of: silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2- methoxybenzenetellurolate, copper 2-methoxybenzenethiolate, silver (I) 3- methoxybenzenethiolate, silver 3-methoxybenzeneselenolate, silver 3- methoxybenzenetellurolate, copper 3-methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver (I) 4-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver terphenylthiolate, silver 2,6-dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, silver cyclohexyl thiolate, a silver (I) 1-β-D-glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2- Page 34 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, and silver 4-heptanethiolate.

13. The composition of claim 9, wherein the metal organic chalcogenolate polymer has a one-dimensional crystalline structure, and wherein R is an organic ligand selected from ortho- (C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, 2,6-dimethylphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group and a secondary alkyl.

14. The composition of claim 13, wherein M is Cu, Ag or Au.

15. The composition of claim 14, wherein M is Ag and E is S.

16. The composition of claim 13, wherein the polymer is selected from the group consisting of: silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2- methoxybenzenetellurolate, copper 2-methoxybenzenethiolate, silver (I) 3- methoxybenzenethiolate, silver 3-methoxybenzeneselenolate, silver 3- methoxybenzenetellurolate, copper 3-methoxybenzenethiolate, silver (I) 3-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6- dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, silver cyclohexyl thiolate, a silver (I) 1-β-D-glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2-propanethiolate, silver 2-butanethiolate, silver 2- pentanethiolate, silver 3-hexanethiolate, and silver 4-heptanethiolate.

17. The composition of claim 9, wherein the composition is in a form of a coating or a film.

18. A device comprising a metal organic chalcogenolate polymer having formula I: [M-E-R]∞(I) wherein M is a metal; E is S, Se or Te; and R is an organic ligand selected from: -(C6H4)-OCH3, -(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

19. The device of claim 18, wherein M is Cu, Ag or Au.

20. The device of claim 19, wherein M is Ag and E is S.

21. The device of claim 18, wherein the polymer is selected from the group consisting of: silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2- Page 35 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) methoxybenzenetellurolate, copper 2-methoxybenzenethiolate, silver (I) 3- methoxybenzenethiolate, silver 3-methoxybenzeneselenolate, silver 3- methoxybenzenetellurolate, copper 3-methoxybenzenethiolate, silver (I) 4- methoxybenzenethiolate, silver (I) 2-methyl mercaptobenzoate, silver (I) 3-methyl mercaptobenzoate, silver (I) 4-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver terphenylthiolate, silver 2,6-dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, silver cyclohexyl thiolate, silver (I) 1-β-D-glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2- propanethiolate, silver 2-butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, or silver 4-heptanethiolate.

22. The device of claim 18, wherein the metal organic chalcogenolate polymer has a one-dimensional crystalline structure, and wherein R is an organic ligand selected from ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, 2,6-dimethylphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group and a secondary alkane.

23. The device of claim 22, wherein M is Cu, Ag or Au.

24. The device of claim 23, wherein M is Ag and E is S.

25. The device of claim 22, wherein the polymer is selected from the group consisting of: silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2- methoxybenzenetellurolate, copper 2-methoxybenzenethiolate, silver (I) 3- methoxybenzenethiolate, silver 3-methoxybenzeneselenolate, silver 3- methoxybenzenetellurolate, copper 3-methoxybenzenethiolate, silver (I) 2-methyl mercaptobenzoate, silver (I) 3-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6-dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, silver cyclohexyl thiolate, a silver (I) 1-β-D- glucose thiolate, a silver (I) 1-β-D-galactose thiolate, silver 2-propanethiolate, silver 2- butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, and silver 4-heptanethiolate.

26. The device of claim 18, wherein the is a semiconductor or a solar cell.

27. A method for preparing a crystalline metal organic chalcogenolate polymer, the method comprising reacting a metal precursor and a chalcogenide with a solvent, the chalcogenide comprising a chalcogen precursor selected from S, Se and Te, and an organic ligand, wherein Page 36 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) the organic ligand is selected from ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)- CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondaryof claim 27, wherein the metal precursor is Ag, Au or Cu.

29. The method of claim 28, wherein the organic ligand is selected from ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, a 1- β-D-glucose, a 1-β-D-galactose, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, and 4-heptyl.

30. The method of claim 27, wherein the solvent is selected from methanol, ethanol, acetone, isopropyl alcohol, water and mixtures thereof.

31. The method of claim 27, wherein a reaction temperature is from about room temperature to about 90°C.

32. A method for preparing a metal organic chalcogenolate polymer having a 2- dimensional crystalline structure, the method comprising reacting a metal organic chalcogenolate having a 1-dimensional crystalline structure and a dichalcogenide, the dichalcogenide comprising a chalcogen precursor selected from S, Se and Te, and an organic ligand, wherein the organic ligand is an aryl group or an n-alkyl group.

33. The method of claim 32, wherein the metal precursor is Ag, Au or Cu.

34. The method of claim 33, wherein the aryl group is a phenyl, biphenyl or a terphenyl.

35. The method of claim 33, wherein the n-alkyl group is selected from ethyl, propyl, butyl, pentyl, hexy, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.

36. The method of claim 32, wherein the metal organic chalcogenolate having a 1- dimensional crystalline structure has formula I: [M-E-R]∞ (I) where M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, ortho-(C6H4)-CO2CH3, meta-(C6H4)-CO2CH3, a carbohydrate group and a secondary alkane. Page 37 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) 37. The method of claim 36, wherein the metal organic chalcogenolate having a 1- dimensional crystalline structure is selected from silver (I) 2-methoxybenzenethiolate, silver 2-methoxybenzeneselenolate, silver 2-methoxybenzenetellurolate, copper 2- methoxybenzenethiolate, silver (I) 3-methoxybenzenethiolate, silver 3- methoxybenzeneselenolate, silver 3-methoxybenzenetellurolate, copper 3- methoxybenzenethiolate, silver (I) 2-methyl mercaptobenzoate, silver (I) 3-methyl mercaptobenzoate, silver 2-chlorobenzenethiolate, silver 2-bromobenzenethiolate, silver 2,6- dimethylbenzenethiolate, silver cyclopropyl thiolate, silver cyclobutyl thiolate, silver cyclopentyl thiolate, or silver cyclohexyl thiolate silver 2-propanethiolate, silver 2- butanethiolate, silver 2-pentanethiolate, silver 3-hexanethiolate, or silver heptanethiolate.

38. The method of claim 32, further comprising a displacement solvent.

39. The method of claim 32, wherein a reaction temperature is from room temperature to about 90°C.

40. A method for producing one or more qubits, comprising delivering a spatial array of pulses to create entangled polaritons / excitons in a metal organic chalcogenolate polymer having formula I: [M-E-R]∞(I) wherein M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)- OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)-CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.

41. The method of claim 40, wherein a focal point of the spatial array of pulses generates a condensate which functions as a qubit.

42. The method of claim 41, wherein an operation of the qubit is managed through at least one of phase and amplitude control of the condensate.

43. The method of claim 40, wherein the entangled polaritons / excitons are controlled through control of polariton-polariton interaction. Page 38 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) 44. The method of claim 43, wherein the polariton-polariton interaction is controlled by the separation between spatial focal points.

45. The method of claim 40, wherein foci of the spatial array of pulses is generated using a spatial light modulator (SLM) with an intertwined, randomly distributed phase mask and a focusing element.

46. A programmable quantum computer assembled, in whole or in part, from the qubit formed by the method of claim 41.

47. The programmable quantum computer of claim 46, wherein the metal organic chalcogenolate polymer is configured to facilitate on-demand quantum computing.

48. A system for fabrication of entangled polaritons / excitons, comprising: (a) a laser system, (b) a spatial light modulator, (c) a cryogenically cooled chamber, and (d) a metal organic chalcogenolate polymer having formula I: [M-E-R]∞ (I) wherein M is a metal; E is S, Se or Te; and R is an organic ligand selected from: ortho-(C6H4)-OCH3, meta-(C6H4)-OCH3, meta-(C6H4)-CO2CH3, para-(C6H4)- CO2CH3, 2,6-dimethylphenyl, triphenyl, chloro-phenyl, bromo-phenyl, a cycloalkyl, a carbohydrate group, and a secondary alkyl.MOCha materials.

49. The system of claim 48, wherein the laser system is operated at an energy level and pulse duration that is selected based on the metal organic chalcogenolate polymer.

50. The system of claim 48, wherein the laser system delivers pulses that are split into two beam path that include a first beam path that is directed to the spatial light modulator and a second beam path that functions to probe the metal organic chalcogenolate polymer. Page 39 of 41ME150163641v.1Attorney Docket: 98121.00385 (24-023) 51. The system of claim 48, further comprising a pulse shaper and an optical parametric amplifier. Page 40 of 41ME150163641v.1

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