Sublimable compounds, process for their preparation and applications thereof

Abstract

The present disclosure describes to a compound of formula I and to a process for preparing the compound of formula I. The compound of formula I is sublimable and highly conductive. The compound of formula I is used for p-type doping of organic semiconductors and in electronic and optoelectronic devices.

Description

[0001] “SUBLIMABLE COMPOUNDS, PROCESS FOR THEIR PREPARATION AND APPLICATIONS THEREOF”

[0002] TECHNICAL FIELD

[0003] The present disclosure relates generally to the field of organic electronics. More particularly, the present disclosure relates to compounds having sublimable properties which function as effective p-type dopants for optoelectronic devices. The present disclosure also relates to process of preparation of said compounds as well as their applications.

[0004] BACKGROUND OF THE DISCLOSURE

[0005] Organic semiconductors (OSCs) are being used in various optoelectronic devices such as organic light-emitting devices, organic transistors and organic photovoltaic devices. OSC thin films are made from small molecules or polymers with extended conjugations. Organic semiconductor (OSC) based devices are lightweight, need low-cost production, low-temperature processing and show mechanical flexibility. Organic semiconductor materials are often used as transport layers such as halide perovskite based solar cells. Because of these properties, OSCs are used in many emerging classes of electronic devices. Often electronic doping is used to improve the charge carrying capacity of organic thin-films by increasing the number of charge carriers and filling the electronic traps. A large range of p-type and n-type molecular dopants have been used for doping in OSCs. The challenges with the current class of dopants are poor doping efficiency, doping instability, and lack of clean doping.

[0006] In perovskite solar cells, the most commonly used p-type dopant for the hole transport layer (HTL) SpiroOMeTAD is ambient oxygen molecules, followed by anion exchange with the additive LiTFSI. The LiTFSI doping process is inefficient, time-consuming (overnight), and leaves a huge amount of Li salt in the system. Due to inefficient processes, the doping process requires a huge amount of LiTFSI, usually 66.6 mol% of HTL Spiro. Additionally, due to poor solubility, this doping process requires tertiary butyl pyridine (tBP) as an additive for solubility. In the long run, LiTFSI causes degradation of the perovskite layer of solar cells. Migration of metal ions of dopants, like in LiTFSI, affects the working of other layers of solar cell devices and hampers their durability.

[0007] Thus, there is a need for novel compounds which are sublimable, function as highly efficient p-type dopants and overcome the limitations of the p-type dopants known in the art. The present disclosure attempts to address this need. SUMMARY OF THE DISCLOSURE

[0008] Accordingly, the present disclosure provides a compound of formula I:

[0009]

[0010] Formula I

[0011] wherein

[0012] ‘X’ is selected from a group comprising but limiting to halogen, -CH(Ph)2, -CF3, NO2, -(CH2)n-CH3 wherein n ranges from 1 to 12, -CeFs, -CeH5-CF3, and -C6H3-(CF3).

[0013] In another aspect, the present disclosure provides a process for preparing compound of formula I comprising:

[0014] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene, followed by heating to obtain the compound of formula I (BCF-X2DHBQ).

[0015] In yet another aspect, the present disclosure provides use of the compound of formula I as a p-type dopant.

[0016] In still another aspect, the present disclosure provides an organic semiconductor thin film doped with said compound of formula I.

[0017] BRIEF DESCRIPTION OF THE ACCOMPANYING FIGURES

[0018] In order that the disclosure may be readily understood and put into practical effect, reference will now be made to exemplary embodiments as illustrated with reference to the accompanying figures. The figures together with description below, are incorporated in and form part of the specification, and serve to further illustrate the embodiments and explain various principles and advantages, where:

[0019] Figure 1 illustrates a plot describing the19F NMR of F2DHBQ in acetonitrile-d3 at room temperature.

[0020] Figure 2 illustrates a plot describing the 'H NMR spectrum of Ph₂DHBQ in CDCl₃ at room temperature.

[0021] Figure 3 illustrates a plot describing the19F NMR spectrum of BCF-F2DHBQ in CDCl3at room temperature.

[0022] Figure 4 illustrates the molecular structure of BCF-F2DHBQ with thermal ellipsoids at 50% probability level.

[0023] Figure 5 illustrates a plot describing the19F NMR spectrum of BCF-ChDHBQ in CDCl3at room temperature.

[0024] Figure 6 illustrates the molecular structure of BCF-ChDHBQ with thermal ellipsoids at 50% probability level.

[0025] Figure 7 illustrates a plot describing the 'H NMR spectrum of BCF-Ph₂DHBQ in CDCl₃ at room temperature.

[0026] Figure 8 illustrates a plot describing the19F NMR spectrum of BCF-PI12DHBQ in CDCl3at room temperature.

[0027] Figure 9 illustrates the molecular structure of BCF-Ph₂DHBQ with thermal ellipsoids at 50% probability level. Hydrogen atoms have been omitted for clarity.

[0028] Figure 10 illustrates the crystal structure of salt having SpiroOmeTAD+ and BCF-Cl₂DHBQ⁻ with thermal ellipsoids at 50% probability level (Hydrogen atoms have been omitted for clarity). Figure 11 illustrates plots describing EPR (Electron paramagnetic resonance spectroscopy) of pristine spiro and doped spiro in solution state at room temperature, wherein-(a) doped with BCF-ChDHBQ; (b) doped with BCF-F2DHBQ; and (c) doped with BCF-Ph2DHBQ.

[0029] Figure 12 illustrates the crystal structure of salt having SpiroOmeTAD+and BCF-Ph2DHBQ⁻ with thermal ellipsoids at 50% probability level (Hydrogen atoms have been omitted for clarity).

[0030] Figure 13 illustrates plots, wherein - (a) describes I-V (Current- Voltage) graph of thin film of undoped Spiro-OMeTAD and Spiro-OMeTAD doped with BCF-X2DHBQ and its comparison with LiTFSI; (b) describes electrical conductivity of undoped Spiro-OMeTAD and films doped with 5 mol% BCF-X2DHBQ, in comparison with 5 mol% F4TCNQ and LiTFSI (66 mol%); (c) describes conductivity of PTAA doped with conventional p-type dopant EtTCNQ (5 mole %), measured under thermal stress at 100 °C over time; and (d) describes conductivity of PTAA doped with BCF-X2DHBQ (5 mole %) under the same 100 °C thermal stress conditions as a function of time.

[0031] Figure 14 illustrate plots describing I-V characteristics of HTMs doped with BCF-F2DHBQ.

[0032] Figure 15 illustrate plots describing I-V characteristics of HTMs doped with BCF-ChDHBQ.

[0033] Figure 16 illustrate plots describing I-V characteristics of HTMs doped with BCF-Ph2DHBQ.

[0034] Figure 17 illustrates performance of perovskite solar cells. In the control device, the hole transport layer (HTL) is doped with LiTFSI (66 mole% ), while in the target device, the HTL is doped with BCF-Ph₂DHBQ (5 mol%). (a) illustrates schematic diagram of the perovskite solar cell structure; (b) describes J-V curves of the target device; and (c) describes continuous power conversion efficiency (PCE) tracking of the control and target devices.

[0035] Figure 18 illustrates the performance of red OLEDs. In the control device, the hole transport layer (HTL), TAPC, is undoped and an HATCN layer is inserted between ITO and TAPC to assist hole injection. In contrast, in the target device, TAPC is doped with BCF-F2DHBQ, eliminating the need for an HATCN layer, (a) illustrates schematic diagram of the target OLED device structure; (b) describes L-V characteristics of the target and control devices; and (c) describes comparison of the external quantum efficiency (EQE) for the target and control structures. Figure 19 illustrates the performance of green-blue OLEDs. In the control device, the hole transport layer (HTL), a-NPD, is undoped. In contrast, the target device includes an additional sublayer of a-NPD doped with BCF-F2DHBQ beneath the pristine a-NPD to enhance hole injection, (a) illustrates schematic diagram of the target OLED device structure; (b) describes L-V characteristics of the target and control devices; (c) describes statistical comparison of the external quantum efficiency (EQE) for the target and control structures.

[0036] DESCRIPTION OF THE DISCLOSURE

[0037] It is to be understood that the present disclosure is not limited in its application to the details of compound and process set forth in the following description. The present disclosure is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.

[0038] In view of the limitations discussed above, the present disclosure provides a compound of formula I that is sublimable and functions as a p-type dopant for optoelectronic devices.

[0039] However, before describing the invention in greater detail, it is important to take note of the common terms and phrases that are employed throughout the present disclosure for better understanding of the technology provided herein.

[0040] Definitions

[0041] Dopants are used to add charge carriers to the semiconductor by creating either an excess or a deficiency of electrons around the foreign atom. P-type dopants for organic semiconductors can be an organic, organometallic, metal complexes that remove electrons from the host material.

[0042] As used herein, the term ‘comprising’ when placed before the recitation of steps in a method means that the method encompasses one or more steps that are additional to those expressly recited, and that the additional one or more steps may be performed before, between, and / or after the recited steps. For example, a method comprising steps a, b, and c encompasses a method of steps a, b, x, and c, a method of steps a, b, c, and x, as well as a method of steps x, a, b, and c. Furthermore, the term “comprising” when placed before the recitation of steps in a method does not (although it may) require sequential performance of the listed steps, unless the content clearly dictates otherwise. For example, a method comprising steps a, b, and c encompasses, for example, a method of performing steps in the order of steps a, c, and b, the order of steps c, b, and a, and the order of steps c, a, and b, etc.

[0043] With respect to the use of substantially any plural and / or singular terms herein, those having skill in the art can translate from the plural to the singular and / or from the singular to the plural as is appropriate to the context and / or application. The various singular / plural permutations may be expressly set forth herein for sake of clarity. The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results.

[0044] Throughout this specification, the word “comprise”, or variations such as “comprises” or “comprising” or “containing” or “has” or “having”, or “including but not limited to” wherever used, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

[0045] Reference throughout this specification to “some embodiments”, “one embodiment” or “an embodiment”, “a preferred embodiment”, “a non-limiting embodiment” or “an exemplary embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment may be included in at least one embodiment of the present disclosure. Thus, the appearances of the phrases “in some embodiments”, “in one embodiment” or “in an embodiment”, “a preferred embodiment”, “a non-limiting embodiment” or “an exemplary embodiment” in various places throughout this specification may not necessarily all refer to the same embodiment. It is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.

[0046] In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined can be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous can be combined with any other feature or features indicated as being preferred or advantageous. The terms ‘about’ or ‘approximately’ as used herein when referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, are meant to encompass variations of and from the specified value, such as variations of + / -10% or less, + / -5% or less, + / -1% or less, and + / -0.1% or less of and from the specified value, insofar such variations are appropriate to perform in the disclosed invention. It is to be understood that the value to which the modifier ‘about’ or ‘approximately’ refers is itself also specifically, and preferably, disclosed.

[0047] The use of any and all examples, or exemplary language (e.g., “such as”) provided with respect to certain embodiments herein is intended merely to better illustrate the disclosure and does not pose a limitation on the scope of the disclosure otherwise claimed.

[0048] Throughout this specification, the term ‘a combination thereof, ‘combinations thereof or ‘any combination thereof or ‘any combinations thereof are used interchangeably and are intended to have the same meaning, as regularly known in the field of patent disclosures.

[0049] As used herein, the term 'compound(s)' comprises the compounds disclosed in the present disclosure.

[0050] Disclosure

[0051] The present disclosure provides a compound of formula I

[0052]

[0053] Formula I

[0054] wherein

[0055] ‘X’ is selected from a group comprising but limiting to halogen, -CH(Ph)2, -CF3, NO2, -(CH2)n-CH3 wherein n ranges from 1 to 12, -CeFs, -CeH5-CF3, and -C6H3-(CF3). In some embodiments of the present disclosure, ‘X’ is a halogen selected from a group comprising F, Cl, Br and I.

[0056] In an embodiment, the compound of formula I can be represented as BCF-X2DHBQ

[0057] In some exemplary non-limiting embodiments of the present disclosure, ‘X’ is F or Cl.

[0058] Accordingly, in some embodiments, the present disclosure provides a compound of formula IA:

[0059]

[0060] Formula I A

[0061] Accordingly, in some embodiments, the present disclosure provides a compound of formula IB:

[0062]

[0063] Formula IB:

[0064] In some embodiments of the present disclosure, ‘X’ is -CH(Ph)2.

[0065] Accordingly, in some embodiments, the present disclosure provides a compound of formula IC:

[0066]

[0067] Formula IC:

[0068] In some embodiments of the present disclosure, the compound of formula I is sublimable at a temperature ranging from about 200-300°C, including values and ranges therebetween and at a pressure ranging from about 0.010-0.02 torr, including values and ranges therebetween.

[0069] For example, the compound of formula I is sublimable at a temperature of about 200-300°C, about 200-270°C, about 200-250°C, about 200-220°C, about 220-300°C, about 220-270°C, about 220-250°C, about 250-300°C, about 250-270°C, about 270-300°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, or about 300°C; the compound of formula I is sublimable at a pressure of about 0.010-0.02 torr, about 0.010-0.015 torr, about 0.15-0.02 torr, about 0.010 torr, about 0.011 torr, about 0.012 torr, about 0.013 torr, about 0.014 torr, about 0.015 torr, about 0.016 torr, about 0.017 torr, about 0.018 torr, about 0.019 torr, or about 0.020 torr.

[0070] In some exemplary, non-limiting embodiments of the present disclosure, the compound of formula I is sublimable at a temperature ranging from about 200-250°C, at pressure of about 0.015 torr.

[0071] In some exemplary, non-limiting embodiments of the present disclosure, the compound of formula IA is sublimable at a temperature of about 200°C, at pressure of about 0.015 torr.

[0072] In some exemplary, non-limiting embodiments of the present disclosure, the compound of formula IB is sublimable at a temperature of about 220°C, at pressure of about 0.015 torr.

[0073] In some exemplary, non-limiting embodiments of the present disclosure, the compound of formula IC is sublimable at a temperature of about 250°C, at pressure of about 0.015 torr. The present disclosure also provides a process for preparing the compound of formula I, encompassing the compound of Formula IA, IB and IC. Accordingly, although the subsequent embodiments relate to a process for preparing the compound of formula I, the compounds of formula I are as described in the previous embodiments and are not being reiterated for the sake of brevity but fall wholly within the scope of the present embodiments.

[0074] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0075] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene and heating to obtain the compound of formula I (BCF-X2DHBQ).

[0076] In some embodiments, the 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) are added at a molar ratio of about 1:2 to about 1:4, including values and ranges therebetween, such as about 1:2, about 1:3, or about 1:4.

[0077] In some embodiments, dichlorobenzene is added at a concentration of about 40-50 molar % with respect to the weight / amount of X2DHBQ, including values and ranges therebetween, such as about 40-50%, about 40-45%, about 45-50%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49% or about 50% with respect to the weight / amount of X2DHBQ.

[0078] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0079] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1:2 to about 1:4, followed by heating to obtain the compound of formula I (BCF-X2DHBQ).

[0080] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0081] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1:2 to about 1:4, followed by heating to obtain the compound of formula I (BCF-X2DHBQ); wherein di chlorobenzene is added at a concentration of about 40-50 molar % with respect to the weight / amount of X2DHBQ. In some embodiments, the heating is carried out at a temperature ranging from about 100-180°C, including values and ranges therebetween for a time period ranging from about 1-30 hours, including values and ranges therebetween.

[0082] For example, the heating is carried out at a temperature of about 100-180°C, about 100-160°C, about 100-150°C, about 100-135°C, about 100-115°C, about 115-180°C, about 115-165°C, about 115-150°C, about 115-135°C, about 115-150°C, about 130-180°C, about 130-160°C, about 135-150°C, about 150-180°C, about 150-160 about 150-160°C, about 100°C, about 105°C, about 110°C, about 115°C, about 120°C, about 125°C, about 130°C, about 135°C, about 140°C, about 145°C, about 150°C, about 155°C, about 160°C, about 165°C, about 170°C, about 175°C, or about 180°C; for time period of about 1-30 hours, about 1-27 hours, about 1-24 hours, about 1-20 hours, about 1-15 hours, about 1-10 hours, about 1-5 hours, about 5-30 hours, about 5-27 hours, about 5-24 hours, about 5-20 hours, about 5-15 hours, about 5-10 hours, about 10-30 hours, about 10-27 hours, about 10-24 hours, about 10-20 hours, about 10-15 hours, about 15-30 hours, about 15-27 hours, about 15-24 hours, about 15-20 hours, about 20-30 hours, about 20-27 hours, about 20-24 hours, about 24-30 hours, about 24-27 hours, about 27-30 hours, about 1 hour, about 2 hours, about 5 hours, about 7 hours, about 10 hours, about 12 hours, about 15 hours, about 17 hours, about 19 hours, about 20 hours, about 21 hours, about 22 hours, about 23 hours, about 24 hours, about 25 hours, about 26 hours, about 27 hours, about 28 hours, about 29 hours, or about 30 hours.

[0083] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0084] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene followed by heating to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula I (BCF-X2DHBQ).

[0085] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0086] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula I (BCF-X2DHBQ). Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0087] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula I (BCF-X2DHBQ); wherein di chlorobenzene is added at a concentration of about 40-50 molar % with respect to the weight / amount of X2DHBQ.

[0088] In some exemplary non-limiting embodiments, the process for preparing the compound of formula I comprises:

[0089] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature of about 135°C, for time period of about 24 hours to obtain the compound of formula I (BCF-X2DHBQ).

[0090] Provided below is a scheme for preparing the compound of formula I of the present disclosure, according to an exemplary non-limiting embodiment.

[0091] Dichlorobenzene 135°C -2 C6F5H

[0092]

[0093] In some non-limiting embodiments, the process further comprises heating the compound of formula I to a temperature ranging from about 130-250°C, including values and ranges therebetween, for removing trace amount of starting materials, i.e., X2DBHQ, BCF, dichlorobenzene or a combination thereof. For example, the compound of formula I is heated to a temperature of about 130-250°C, 130-200°C, 130-160°C, 160-250°C, about 160-200°C, about 200-250°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, or about 250°C. Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0094] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture; heating the mixture to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula I (BCF-X2DHBQ); and heating the compound of formula I to a temperature of about 130-250°C.

[0095] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula I, comprising:

[0096] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture; heating the mixture to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula I (BCF-X2DHBQ); wherein dichlorobenzene is added at a concentration of about 40-50 molar % with respect to the weight / amount of X2DHBQ; and

[0097] heating the compound of formula I to a temperature of about 130-250°C.

[0098] In some exemplary non-limiting embodiments, the process for preparing the compound of formula I comprises:

[0099] adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture; heating the mixture to a temperature of about 135°C, for time period of about 24 hours to obtain the compound of formula I (BCF-X2DHBQ); and

[0100] heating the compound of formula I to a temperature of about 200°C.

[0101] In some embodiments, based on the functional group ‘X’ in X2DHBQ, the process of the present disclosure results in the synthesis of compound of formula IA, compound of formula IB or compound of formula 1C.

[0102] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula IA, comprising adding 2,5-dihydroxy-3,6-difluoro-l,4-benzoquinone (F2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene and heating to obtain the compound of formula IA (BCF-F2DHBQ).

[0103] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula IA, comprising:

[0104] adding 2,5-dihydroxy-3,6-difluoro-l,4-benzoquinone (F2DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1: 2 to about 1:4 followed by heating to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula IA (BCF-F2DHBQ).

[0105] In some exemplary non-limiting embodiments, the process for preparing the compound of formula IA comprises:

[0106] adding 2,5-dihydroxy-3,6-difluoro-l,4-benzoquinone (F2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature ranging of about 135°C, for time period of about 24 hours to obtain the compound of formula IA (BCF-F2DHBQ).

[0107] In some embodiments, the present disclosure provides a process for preparing the compound of formula IA, comprising:

[0108] adding 2,5-dihydroxy-3,6-difluoro-l,4-benzoquinone (F2DHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture;

[0109] heating the mixture to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula IA (BCF-F2DHBQ); and heating the compound of formula IA to a temperature of about 130-250°C.

[0110] In some exemplary non-limiting embodiments, the process for preparing the compound of formula IA comprises:

[0111] adding 2,5-dihydroxy-3,6-difluoro-l,4-benzoquinone (F2DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1: 2 to about 1:4 to obtain a mixture;

[0112] heating the mixture to a temperature of about 135 °C, for time period of about 24 hours to obtain the compound of formula IA (BCF-F2DHBQ); and

[0113] heating the compound of formula IA to a temperature of about 200°C. Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula IB, comprising adding 2,5-dihydroxy-3,6-dichloro-l,4-benzoquinone (ChDHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene and heating to obtain the compound of formula IB (BCF-ChDHBQ).

[0114] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula IB, comprising:

[0115] adding 2,5-dihydroxy-3,6-dichloro-l,4-benzoquinone (ChDHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula IB (BCF-ChDHBQ).

[0116] In some exemplary non-limiting embodiments, the process for preparing the compound of formula IB comprises:

[0117] adding 2,5-dihydroxy-3,6-dichloro-l,4-benzoquinone (ChDHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4, followed by heating to a temperature ranging of about 135°C, for time period of about 24 hours to obtain the compound of formula IB (BCF-ChDHBQ).

[0118] In some embodiments, the present disclosure provides a process for preparing the compound of formula IB, comprising:

[0119] adding 2,5-dihydroxy-3,6-dichloro-l,4-benzoquinone (ChDHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1: 2 to about 1:4 to obtain a mixture;

[0120] heating the mixture to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula IB (BCF-ChDHBQ); and heating the compound of formula IB to a temperature of about 130-250°C.

[0121] In some exemplary non-limiting embodiments, the process for preparing the compound of formula IB comprises:

[0122] adding 2,5-dihydroxy-3,6-dichloro-l,4-benzoquinone (ChDHBQ) and tris(pentafluorophenyl)borane (BCF) to di chlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture; heating the mixture to a temperature of about 135 °C, for time period of about 24 hours to obtain the compound of formula IB (BCF-ChDHBQ); and

[0123] heating the compound of formula IB to a temperature of about 200°C.

[0124] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula IC, comprising adding 2,5-Bis(diphenylmethyl)-3,6-dihydroxy-2,5-cy cl ohexadiene- 1,4-dione (PI12DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene and heating to obtain the compound of formula IC (BCF-Ph2DHBQ).

[0125] Accordingly, in some embodiments, the present disclosure provides a process for preparing the compound of formula IC, comprising:

[0126] adding 2, 5-Bis(diphenylmethyl)-3,6-dihydroxy-2,5-cyclohexadiene-l, 4-dione (PI12DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula IC (BCF-Ph2DHBQ).

[0127] In some exemplary non-limiting embodiments, the process for preparing the compound of formula IC comprises:

[0128] adding 2, 5-Bis(diphenylmethyl)-3,6-dihydroxy-2,5-cyclohexadiene-l, 4-dione (PI12DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1:2 to about 1:4 followed by heating to a temperature ranging of about 135°C, for time period of about 24 hours to obtain the compound of formula IC (BCF-Ph2DHBQ).

[0129] In some embodiments, the present disclosure provides a process for preparing the compound of formula IC, comprising:

[0130] adding 2, 5-Bis(diphenylmethyl)-3,6-dihydroxy-2,5-cyclohexadiene-l, 4-dione (PI12DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture;

[0131] heating the mixture to a temperature ranging from about 100-180°C, for time period ranging from about 1-30 hours to obtain the compound of formula IC (BCF-PI12DHBQ); and heating the compound of formula IC to a temperature of about 130-250°C.

[0132] In some exemplary non-limiting embodiments, the process for preparing the compound of formula IC comprises: adding 2, 5-Bis(diphenylmethyl)-3,6-dihydroxy-2,5-cyclohexadiene-l, 4-dione (PI12DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene at a molar ratio of about 1:2 to about 1:4 to obtain a mixture;

[0133] heating the mixture to a temperature of about 135 °C, for time period of about 24 hours to obtain the compound of formula IC (BCF-PI12DHBQ); and

[0134] heating the compound of formula IC to a temperature of about 200°C.

[0135] The compound of formula I of the present disclosure is sublimable and exhibits high conductivity. Additionally, the compound of formula I is thermally stable at a temperature ranging from about 25 to 350°C, including values and ranges therebetween, such as about 25-350°C, about 25-300°C, about 25-250°C, about 25-200°C, about 25-150°C, about 25-100°C, about 25-75°C, about 25-50°C, about 50-350°C, about 50-300°C, about 50-250°C, about 50-200°C, about 50-150°C, about 50-100°C, about 50-75°C, about 75-350°C, about 75-300°C, about 75-250°C, about 75-200°C, about 75-150°C, about 75-100°C, about 100-350°C, about 100-300°C, about 100-250°C, about 100-200°C, about 100-150°C, about 150-350°C, about 150-300°C, about 150-250°C, about 150-200°C, about 200-350°C, about 200-300°C, about 200-250°C, about 250-350°C, about 250-300°C, about 300-350°C, about 25°C, about 50°C, about 75°C, about 100°C, about 125°C, about 150°C, about 175°C, about 200°C, about 225°C, about 250°C, about 275°C, about 300°C, about 325°C, or about 350°C. Accordingly, the compound of formula I of the present disclosure may be used in any application wherein these properties are required.

[0136] In some embodiments, the compound of formula I of the present disclosure is used for p-type doping of organic semiconductors (OSCs).

[0137] Accordingly in some embodiments, the present disclosure provides an organic semiconductor thin film doped with the compound of formula I as described in any one of the previous embodiments.

[0138] In some embodiments, the organic semiconductor thin film is doped with about 0.1 mole% to 20 mole% of the compound of formula I as described in any one of the previous embodiments, including values and ranges therebetween. For example, the organic semiconductor thin film is doped with the compound of formula I at a concentration of about 0.1-20 mole%, about 0.1-15 mole%, about 0.1-10 mole%, about 0.1-7 mole%, about 0.1-5 mole%, about 0.1-3 mole%, about 0.1-1 mole%, about 0.1-0.5 mole%, about 0.5-20 mole%, about 0.5-15 mole%, about 0.5-10 mole%, about 0.5-7 mole%, about 0.5-5 mole%, about 0.5-3 mole%, about 0.5-1 mole%, about 1-20 mole%, about 1-15 mole%, about 1-10 mole%, about 1-7 mole%, about 1-5 mole%, about 1-3 mole%, about 3-20 mole%, about 3-15 mole%, about 3-10 mole%, about 3-7 mole%, about 3-5 mole%, about 5-20 mole%, about 5-15 mole%, about 5-10 mole%, about 5-7 mole%, about 7-15 mole%, about 7-10 mole%, about 10-15 mole%, about 0.1 mole%, about 0.2 mole%, about 0.5 mole%, about 0.7 mole%, about 1 mole%, about 3 mole%, about 5 mole%, about 7 mole%, about 10 mole%, about 12 mole%, about 15 mole%, about 17 mole%, or about 20 mole%.

[0139] Accordingly, in some embodiments, the present disclosure provides an organic semiconductor thin film doped with about 0.1 mole% to 20 mole% of the compound of formula I as described in any one of the previous embodiments. In an embodiment, the organic semiconductor thin film can be doped with the compound of formula IA, the compound of formula IB or the compound of formula IC.

[0140] In some embodiments, the organic semiconductor thin film doped with the compound of formula I of the present disclosure exhibits about 1000 to 50000 times increase in current value, including values and ranges therebetween, such as about 1000-50000 times, about 1000-40000 times, about 1000-30000 times, about 1000-20000 times, about 3000-40000 times, about 5000-30000 times, about 6000-20000 times, about 7000-10000 times, about 10000-50000 times, about 1000 times, about 2000 times, about 3000 times, about 4000 times, about 5000 times, about 6000 times, about 7000 times, about 8000 times, about 9000 times, about 10000 times, about 15000 times, about 20000 times, about 25000 times, about 30000 times, about 35000 times, about 40000 times, about 45000 times, or about 50000 times as compared to pristine / undoped thin film.

[0141] In some embodiments, the organic semiconductor thin film doped with the compound of formula I of the present disclosure exhibits thermal stability up to a temperature of about 100-120°C, including values and ranges therebetween such as about 100-120°C, about 100-105°C, about 100-110°C, about 105-120°C, about 105-110°C, about 110-120°C, about 100°C, about 102°C, about 104°C, about 105°C, about 106°C, about 108°C, about 110°C, about 112°C, about 114°C, about 116°C, about 118°C, or about 120°C. In some embodiments, the compound of formula I of the present disclosure may be used in electronic and optoelectronic devices.

[0142] The foregoing descriptive matter is illustrative of the disclosure and not a limitation. While the present disclosure is susceptible to various modifications and alternative forms, specific aspects thereof have been shown by way of examples and drawings and are described in detail below. However, it should be understood that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and the scope of the invention as defined by the embodiments of the disclosure.

[0143] EXAMPLES

[0144] Materials and Methods

[0145] All air-sensitive experiments were carried out under nitrogen atmosphere. Standard Schlenk techniques and MBraun UNILAB Glovebox were used. Trispentafluorophenylborane, chloranil, tetrafluorobenzoquinone, Lithium Bis(trifluoromethanesulfonyl)imide (LiTFSI), Tetrafluorotetracyanoquinodimethane (F4TCNQ) and anhydrous hexane were purchased from TCI chemicals. 2,5-dihyroxybenzoquinone and anhydrous solvents like toluene and dichlorobenzene were bought from Sigma Aldrich. Spiro-MeOTAD was bought from Lumtec and was used without further purification. Bruker Nano Bay 300 MHz NMR spectrometer was used to record NMR spectra. Reference peaks for 1H and13C{XH} NMR spectra were the peaks of residual protons of the deuterated solvent (1H) or the deuterated solvent itself (^C^H}).

[0146] EXAMPLE 1:

[0147]

[0148] ic Scheme of Precursors

[0149] (a) Synthesis of F2DHBQ (Scheme 1)

[0150] 1,4-di oxane

[0151] NaOH, HC?

[0152]

[0153] F

[0154] Fluoronil F2DHBQ

[0155] Scheme 1: Synthesis of F2DHBQ

[0156] An aqueous solution of NaOH (5.65 M, 40 mL) was added slowly with stirring to a solution of fluoranil (1.37 g, 7.62 mmol) in dioxane (15 mL). The resulting dark brown mixture was stirred at 55-60°C for 5 hours. The reaction mixture was then acidified with HC1 (32%, 20 mL), added slightly in excess, leading to the formation of an orange precipitate. The precipitate was collected by filtration and air-dried. The crude product was dissolved in acetone, forming a red solution with fine white precipitate. The solution was filtered, and the filtrate was concentrated using a rotary evaporator, yielding a crystalline orange-brown precipitate (55% yield).

[0157] This product was recrystallized from hot acetic acid, producing bright orange plates, which were collected by filtration, washed with cold acetic acid, and air-dried. The product was sublimed before use. Final yield: 30%

[0158] The NMR data is provided in figure 1, illustrating19F NMR (300 MHz, CDCl3, 298K): 5 = 158.48 ppm.

[0159] (b) Synthesis of PI12DHBQ (Scheme 2)

[0160]

[0161] DHBQ diphenylmethanoi Ph2DHBQ

[0162] Scheme 2: Synthesis of PI12DHBQ

[0163] DHBQ (2 g, 14.30 mmol), diphenylmethanol (5.5 g, 29.9 mmol), and concentrated H2SO4 (0.5 mL) were dissolved in acetic acid (20 mL). The reaction mixture was refluxed at 155 °C for 1 hour. After reflux, the mixture was cooled to room temperature, resulting in the formation of solid precipitates. These precipitates were collected by vacuum filtration through a glass frit and thoroughly washed with water. The collected solids were then dried overnight at 90 °C. The compound was characterized by 'H NMR (Figure 2). Yield: 95%.

[0164] 'H NMR (300 MHz, CDCl3, 298K): 5 = 7.91 ppm (s, -OH proton on alpha carbon), 7.26 ppm (s, aromatic protons and solvent peak), 5 = 5.69 ppm (s, -CH).

[0165] EXAMPLE 2: Synthesis of Compound of Formula I of the Present Disclosure

[0166]

[0167] (a) Synthesis of Compound 1A (BCF-F2DHBO)

[0168] In nitrogen filled glovebox, 2,5-dihydroxy-3,6-difluoro-l,4-benzoquinone (F2DHBQ) (75 mg, 0.428 mmol) and tris(pentafluorophenyl)borane (450 mg, 0.879 mmol) were taken in 50 mL of anhydrous dichlorobenzene. The mixture was heated at 135°C for 24 hours and the solvent was dried under vacuum to yield a dark greenish-brownish powder. The residue was further heated at 200 °C under high vacuum to remove the trace amount of starting materials. Single crystals were obtained by slow cooling of a hot solution of the compound in toluene. The compound was characterized by19F NMR (Figure 3) and single crystal XRD (Figure 4). Yield: 60%.

[0169] 19F NMR (300 MHz, CDCl3, 298K): 5= -132.89 ppm (m, meta fluorine on aromatic ring), 5= -147.69 ppm (m, broad peak, para fluorine on aromatic ring), 5= -154.17 ppm (s, fluorine on benzoquinone core), 5= -161 ppm (m, ortho fluorine on aromatic ring)

[0170] (b) Synthesis of Compound IB (BCF-ChDHBQ)

[0171] In a N2 filled glove box, 2,5-dihydroxy-3,6-dichloro-l,4-benzoquinone (ChDHBQ) (100 mg, 0.478 mmol) and tris(pentafluorophenyl)borane (502 mg, 0.981 mmol) were taken in 50 mL of anhydrous di chlorobenzene. The mixture was heated at 135°C for 24 hours and the resultant solution was dried under vacuum to yield a dark green powder. The residue was further heated at 200 °C under high vacuum to remove the trace amount of starting materials. Single crystals were obtained by slow cooling of a hot solution of the compound in toluene. The compound was characterized by19F NMR (Figure 5) and single crystal XRD (Figure 6). Yield: 350 mg, 81%.

[0172] 19F NMR (300 MHz, CDCl3, 298K): 5= = -133.45 ppm (d, meta fluorine on aromatic ring), 5= = -150.59 ppm (m, broad peak, para fluorine on aromatic ring), 5= = -160.84 ppm (m, ortho fluorine on aromatic ring)

[0173] (b) Synthesis of Compound 1C (BCF-PI12DH BQ)

[0174] In a N2filled glovebox, Ph2-DHBQ (205.00 mg, 889.32 pmol) and BCF (455.32 mg, 433.83 pmol) were added to 45 ml of anhydrous DCB (ortho-1, 2-dichlorobenzene). The reaction mixture was heated at 135°C for 24 hours and the resultant solution was dried under vacuum to yield dark brownish powder. The residue was further heated at 200 °C under high vacuum to remove the trace amount of starting materials. Yield: 357.00 mg, 307.66 pmol (70.92% with respect to Ph2-DHBQ). Single crystal of the compound was obtained by the vapour diffusion technique using dichloromethane-pentane solvents at room temperature. The compound was characterized by1H NMR (Figure 7)19F NMR (Figure 8) and single crystal XRD (Figure 9).1H NMR (300 MHz, CDCl3, 298K): 5 = 7.187 (s, aromatic protons and solvent peak), 5 = 5.695 (s, -CH).

[0175] 19F NMR (300 MHz, CDCl3, 298K): 5= = -133.87 ppm (m, meta fluorine on aromatic ring), 5= = -152.01 ppm (t, para fluorine on aromatic ring), 5= = -161.65 ppm (m, ortho fluorine on aromatic ring)

[0176] EXAMPLE 3: Sublimable Properties of the Compound of Formula I of the Present Disclosure

[0177]

[0178] The powders of the compounds synthesized in Example 2 were placed in a sublimation set-up and purged with N2, respectively. The set-up was connected to vacuum pump to achieve 0.015 torr vacuum. Using a metal heating element, the temperature was raised to ~ 200°C - ~250°C The materials (powders of the compounds) sublimed from the bottom of the sublimation set-up and collected on the collection tube. The deposited samples were collected from sublimation setup and characterized for their purity and function. The compounds were found to be sublimable at the following temperature and pressure:

[0179] Compound Temperature Pressure (torr)

[0180] BCF-F2DHBQ 200°C 0.015

[0181] BCF-C12DHBQ 220°C 0.015

[0182] BCF-Ph2DHBQ 250°C 0.015

[0183]

[0184] TABLE 1

[0185] EXAMPLE 4: Preparation of Spiro-OMeTAD thin films doped with BCF-Cl2DHBQ Single crystals of organic salt having spiro radical cation and BCF-ChDHBQ radical anion as dopant were grown (provided in Figure 12a). Single crystal XRD confirmed one-electron transfer from spiro to dopant molecule and after electron transfer, there was no structural change in the spiro molecule (Figure 10). Similarly, single crystal XRD of organic salt having spiro radical cation and BCF-Ph2DHBQ radical anion is provided in Figure 12b.

[0186] The charge transfer between OSC and BCF-X2DHBQ was examined with EPR (Electron paramagnetic resonance) spectroscopy. EPR confirmed the charge transfer between the Spiro molecule and dopants BCF-ChDHBQ, BCF-F2DHBQ and BCF-Ph2DHBQ. Doped spiro gave a broad EPR signature at 336.5mT which was absent for undoped spiro (Figure 11). EXAMPLE 5: Preparation of organic thin-film and conductivity measurement Interdigitated gold contacts photolithographically prepared on silicon dioxide (SiO2) was used to measure the electrical conductivity of spiro and doped spiro. The width of the channel was 27 mm and the length of the channel was 20 pm. 60 nm was the thickness of the gold contacts. Keithley 2450 sourcemeter was used to measure current (I)-voltage (V) characteristics. 35mM Spiro-OMeTAD solution was prepared in chlorobenzene. Dopant solutions (compounds of the present disclosure) were prepared in chlorobenzene as shown in Example 2 and added in spiro solution by mol%. The solutions of doped Spiro-OMeTAD were spin-coated onto the substrate at 2000 r.p.m. for 60 seconds and annealed at 50 °C for 2 minutes. Similarly, undoped Spiro-OMeTAD solution was spin-coated on pre-cleaned substrate with the interdigitated gold contacts at a spin speed of 2,000 rpm for 60 seconds.

[0187] I-V (current-voltage) characteristics of doped spiro thin films were measured and the efficiency compared with the commonly used LiTFSI-based doping method for SpiroOmeTAD. At 5 mole% doping with the compounds of the present disclosure, there was -10000 to 50000 times increase in current value as compared to pristine spiro. With respect to LiTFSI doping, there was an increase of 100-500 times (Figure 13a). Additionally, spiro thin films doped with the compounds of the present disclosure exhibited higher electrical conductivity compared to undoped and LiTFSI doped films (Figure 13b). Further, the thermal stability of doped polytriarylamine (PTAA) thin films. As can be seen from Figures 13c and 13d, the PTAA film doped with FMCNQ lost its conductivity within 6 hours of heating at 100 °C, whereas the films doped with the compounds of the present disclosure retained their conductivity for over 100 hours under the same conditions.

[0188] In addition, the current-voltage (I-V) characteristics of other hole-transporting materials (HTMs) was studied and HTMs doped with the compounds of the present disclosure were found to exhibit a 3-5 order of increased magnitude in current, highlighting the strong p-type doping capability of the compounds of the present disclosure. (Figures 14-16)

[0189] EXAMPLE 6: Application in Devices

[0190] The performance of the compounds of the present disclosure as dopants in both perovskite solar cells and OLED devices was studied. In perovskite solar cells, the hole transport layer (HTL) Spiro-OMeTAD doped with BCF-Ph2DHBQ (5 mol%) showed similar efficiency but much better operational stability compared to the control device, where Spiro-OMeTAD was doped with the conventional LiTFSI (66 mol%) and O2 (Figure 17).

[0191] In red OLEDs (Figure 18), doping with BCF-F2DHBQ was found to improve charge injection, leading to higher luminance and quantum efficiency in the target device compared to the control.

[0192] Similarly, in green-blue OLEDs (Figure 19), doping with BCF-F2DHBQ was found to reduce the injection barrier, which resulted in higher luminance and improved quantum efficiency.

[0193] Advantages of the Present Disclosure

[0194] • The compound of formula I of the present disclosure (BCF-X2DHBQ) are sublimable.

[0195] Organic semiconductor thin-films doped with these compounds show thermal stability.

[0196] • The compound of formula I of the present disclosure (BCF-X2DHBQ) act as efficient p-type dopants for organic semiconductors (OSCs).

[0197] • Doped thin films of OSC formed from the compounds of the present disclosure are thermally stable.

[0198] • The sublimable dopants of the present disclosure are bulky in size and give significantly higher conductivity for doped OSC film as compared to other dopants.

[0199] • The compound of formula I of the present disclosure are inexpensive compared to the other p-type dopants already reported.

[0200] • The compounds of the present disclosure as dopants have the potential for their application in efficient electronic devices.

[0201] • Low synthetic cost with high purity, optical tenability, high sublimation compatibility and compatibility with commonly used organic semiconductors renders the compounds of formula I practical and scalable for applications in high-performance optoelectronic devices.

[0202] Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based on the description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known / conventional methods and techniques are omitted so as to not unnecessarily obscure the embodiments herein.

[0203] Numerical ranges stated in the form ‘from x to y’ include the values mentioned and those values that lie within the range of the respective measurement accuracy as known to the skilled person. If several preferred numerical ranges are stated in this form, of course, all the ranges formed by a combination of the different end points are also included.

[0204] As regards the embodiments characterized in this specification, it is intended that each embodiment be read independently as well as in combination with another embodiment. For example, in case of an embodiment 1 reciting 3 alternatives A, B and C, an embodiment 2 reciting 3 alternatives D, E and F and an embodiment 3 reciting 3 alternatives G, H and I, it is to be understood that the specification unambiguously discloses embodiments corresponding to combinations A, D, G; A, D, H; A, D, I; A, E, G; A, E, H; A, E, I; A, F, G; A, F, H; A, F, I; B, D, G; B, D, H; B, D, I; B, E, G; B, E, H; B, E, I; B, F, G; B, F, H; B, F, I; C, D, G; C, D, H; C, D, I; C, E, G; C, E, H; C, E, I; C, F, G; C, F, H; C, F, I, unless specifically mentioned otherwise.

[0205] The foregoing description of the specific embodiments fully reveals the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and / or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments in this disclosure have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.

[0206] While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other modifications in the nature of the disclosure or the preferred embodiments will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.

[0207] Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application. All references, articles, publications, general disclosures etc. cited herein are incorporated by reference in their entireties for all purposes. However, mention of any reference, article, publication, general methodologies etc. cited herein is not, and should not be taken as, an acknowledgment or any form of suggestion that they constitute valid prior art or form part of the common general knowledge in any country in the world.

Claims

WE CLAIM:

1. A compound of Formula IFormula Iwherein:‘X’ is selected from a group comprising of halogen, -CH(Ph)2, -CF3, NO2, -(CH2)n- CH3 wherein n ranges from 1 to 12, -CeFs, -CeHS-CFs, and -C6H3-(CF3).

2. The compound as claimed in claim 1, wherein the compound of Formula I is:Formula I A3. The compound as claimed in claim 1, wherein the compound of Formula I is:BCF-Cl2DHBQFormula IB4. The compound as claimed in claim 1, wherein the compound of Formula I is:Formula IC5. The compound as claimed in any of the claims 1 to 4, wherein the compound is sublimable at temperature ranging from about 200°C to 300°C.

6. A process for preparing the compound of Formula I, comprising:adding 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) to dichlorobenzene; and heating to obtain the compound of Formula I (BCF-X2DHBQ).

7. The process as claimed in claim 6, wherein 3,6-substituted dihydroxybenzoquinone (X2DHBQ) and tris(pentafluorophenyl)borane (BCF) are added at a molar ratio of about 1:2 to 1:4.

8. The process as claimed in claim 6 or 7, wherein dichlorobenzene is added at a concentration of about 40-50 molar % with respect to the amount of X2DHBQ.

9. The process as claimed in claim 6, wherein the heating is carried out at a temperature ranging from about 100°C to 180°C, for a duration ranging from about 1 hour to 30 hours.

10. The process as claimed in claim 6, wherein the process further comprises heating the compound of Formula I to a temperature ranging from about 130°C to 250°C.

11. An organic semiconductor thin film doped with the compound of Formula I as claimed in any one of the claims 1 to 5.

12. The organic semiconductor film as claimed in claim 11, wherein the film is doped with the compound of formula I at a concentration ranging from about 0.1 mole% to 20 mole %.

13. The organic semiconductor film as claimed in claim 11 or 12, wherein the film exhibits about 1000 to 50000 times increase in current value as compared to pristine / undoped thin film.

14. The organic semiconductor film as claimed in any of the claims 11 to 13, wherein the film exhibits thermal stability up to a temperature ranging from about 100 to 120°C.

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