CN106748868B - 有机化合物、光调变组合物、与光调变装置 - Google Patents
有机化合物、光调变组合物、与光调变装置 Download PDFInfo
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- CN106748868B CN106748868B CN201511022262.9A CN201511022262A CN106748868B CN 106748868 B CN106748868 B CN 106748868B CN 201511022262 A CN201511022262 A CN 201511022262A CN 106748868 B CN106748868 B CN 106748868B
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- light modulation
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Classifications
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- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/50—Iso-indoles; Hydrogenated iso-indoles with oxygen and nitrogen atoms in positions 1 and 3
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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Abstract
本发明提供有机化合物、光调变组合物及光调变装置。所述有机化合物具有化学结构：X‑Ar‑X，其中X为 或且Ar为或上述有机化合物的中性态透明，且将酰胺或酰亚胺基团导入芳香胺，除了可增加有机化合物在溶剂中的溶解度之外，还可以提升电化学稳定性。
Description
【技术领域】
本发明涉及有机化合物，更特别涉及包含该有机化合物的光调变组合物 与应用该组合物的光调变装置。
【背景技术】
电致变色相关产品由于其低驱动电压(<3.0V)及双稳态的特性在绿色节 能产业上备受瞩目，全球将此技术视为未来数十年的重要产业，然而电致变 色材料在其中扮演举足轻重的关键角色。目前电致变色材料因为寿命及耐久 性需求，大多使用无机氧化物。然而无机氧化物的制备大多仰赖真空蒸镀、 喷雾热分解、及溅镀等昂贵设备进行镀膜，因成本过高造成目前使用普及率 不高。以材料本质来说，无机氧化物的主要缺点为变色时间缓慢，且电致变 色后的色调较无变化。有机系统中，共轭型高分子可多彩化且变色速度快，但主要缺点为单体成本过高、合成步骤繁杂(多为电聚合方式，其分子量不 易控制)、且受电极线路的限制而不易大面积化。共轭型电致变色高分子因 其共轭长度，中性态大多带有很深的颜色，需施加电压使其颜色由深转淡(非 完全透明)。在人为动态控制选择上，若需透明状态则需驱动给电，造成耗 能的缺点。小分子如三芳香胺及其衍生物具有良好的空穴传导性质，多应用 于OLED的空穴传导层，亦可应用于电致变色的应用上。然而三芳香胺的衍 生物在一般的电解液下溶解性不佳，进而限制了有机小分子在电致变色上的 应用。
综上所述，目前亟需新的化合物以用于电致变色相关产品。
【发明内容】
本发明一实施例提供的有机化合物，其结构为：
X-Ar-X，
其中X为
且R1为烷基；R3为H、烷基、或烷氧基；且R4为H或甲基；
Ar为
Ar’为
Ar”为
Ar3为
且R2为H、烷基、或烷氧基。
本发明一实施例提供的光调变组合物，包括：第一可氧化化合物，为上 述的有机化合物；可还原化合物；电解质；以及溶剂。
本发明一实施例提供的光调变装置，包括：对电极，具有表面具有透明 导电层的第一透明基板，及表面具有透明导电层的第二透明基板，且透明导 电层相对组立；间隙胶，间隙胶系接合于对电极具透明导电层的侧面间，且 对电极与间隙胶间形成密闭空间；以及上述光调变组合物注入填满密闭空 间。
【附图说明】
图1为本发明一实施例中，光调变装置的示意图。
图2为本发明一实施例中，有机化合物的循环伏安谱。
图3为本发明一实施例中，有机化合物的循环伏安谱。
图4为本发明一实施例中，有机化合物于中性态与氧化态的穿透光谱。
图5为本发明一实施例中，有机化合物于中性态与氧化态的穿透光谱。
图6为本发明一实施例中，光调变装置于开关状态的穿透光谱。
图7为本发明一实施例中，光调变装置于开关循环后的穿透光谱。
图8为本发明一实施例中，光调变装置于施加不同电压后的穿透光谱。
【符号说明】
11、19 透明基板；
13、17 透明导电层；
14 间隙胶；
15 光调变组合物。
【具体实施方式】
一般的三芳香胺衍生物(包含五苯二胺及多苯二胺)在有机电解液中溶 解性不佳，加工上多需要高温蒸镀而限制了它在溶液型的电致变色上的应 用。为了简化制程同时保有三芳香胺的电致变色特性，将含有烷链的酰胺基 或酰亚胺基导入三芳香胺结构中，以有效提升三芳香胺于电解液中的溶解性 以利加工，并可提升其退色时的反应速度。就色彩调控部分，搭配其他的可 氧化化合物，亦可达到多彩效果。
本发明一实施方式提供的光调变化合物，其结构为：X-Ar-X，
其中X为
且R1为烷基；R3为H、烷基、或烷氧基；且R4为H或甲基；
Ar为
Ar’为
Ar”为
Ar3为 且R2为H、烷基、或烷氧基。
在一实施方式中，可根据文献J.Polym.Sci.Part A:Polym.Chem.2006, 44,pp4579-4592中的合成方法去制备中间二硝基产物，并经由还原反应得到 二胺单体。上述反应流程图如式1或式2所示。之后取羧酸或酸酐与二胺单体 反应即得有机化合物。在式1与式2中，Ar’、Ar”、与R2的定义同前述。上述 有机化合物除了可应用于电致变色元件之外，亦用于氧化还原感测器、半导 体、太阳能电池、有机电发光元件、非线性材料等等中具空穴传输特性的化 合物。
在一实施方式中，有机化合物的结构如式3所示。在式3中，R5为C1-8烷 基。
在一实施方式中，有机化合物的结构如式4所示。在式4中，R4为H或甲 基。
在一实施方式中，有机化合物的结构如式5所示。在式5中，R6为C1-8烷 基。
在一实施方式中，有机化合物的结构如式6所示。在式6中，R4为H或甲 基。
在一实施方式中，可将上述有机化合物作为可氧化化合物，搭配可还原 化合物、电解质、与溶剂作为光调变组合物。在一实施方式中，可氧化化合 物与可还原化合物的摩尔比例为约1:20至20:1。在一实施方式中，可氧化化 合物与电解质的摩尔比介于1:1至1:20之间。若电解质比例过低，则变色及退 色速度慢。在本发明一实施方式中，电解质至少包含一种惰性传导盐，适当 的惰性传导盐包括锂盐、钠盐及四烷基铵盐。溶剂包括在所选定的电压下对 氧化还原为惰性的所有溶剂，且其不能够离解而形成亲电子基或亲核基，或其本身不会作为足够强的亲电子基或亲核基进行反应，且因此不会与带有颜 色的离子性自由基反应。其实例为碳酸丙烯酯(PC)、γ-丁内脂(GBL)、乙腈、 丙腈、戊二腈、甲基戊二腈、3,3’-氧二丙腈、羟基丙腈、二甲基甲酰胺、N- 甲基四氢吡咯酮、环丁吡(环丁砜，sulfolane)、3-甲基环丁吡或其混合物。 优选为碳酸丙烯酯及其与戊二腈的混合物。且电解质浓度介于0.01M至1.5M 之间。
在一实施方式中，可还原化合物为 或上述的组合，其中R7为C1-10烷基。在本发明另一实施方式中，可氧化化合物可进一步包含其他可 氧化化合物，其结构为 或上述的组合，其中R8为H或烷基。
在本发明一实施方式中，光调变装置包括对电极，包括表面具有透明导 电层的第一透明基板，及表面具有透明导电层的第二透明基板，且第一透明 基板与第二透明基板的透明导电层相对组立。光调变装置亦包含间隙胶接合 于透明导电层的侧面之间，且对电极与该间隙胶间形成密闭空间；以及上述 光调变组合物填满密闭空间。
如图1所示，一对电极包括透明导电层13，位于透明基板11的表面上， 以及透明导电层17，位于透明基板19的表面上，其中透明导电层13与透明导 电层17相对组立，并以间隙胶14接合该对电极，间隙胶位于该对电极具有透 明导电层13及17的侧面间，且该对电极与该间隙胶间形成密闭空间。接着， 经由间隙胶14上保留的孔洞将光调变组合物15填入透明导电层13及17与间 隙胶14之间的空间，再封住孔洞即完成光调变装置。透明基板可由玻璃或塑 胶(例如聚碳酸酯)制成，导电层包含例如氧化铟锡(ITO)、锑-或氟-掺杂的氧 化锡(FTO)、锑-或铝-掺杂的氧化锌、氧化锡。间隙胶可由填隙物及热固性或 光化学上可熟化的粘着剂混合制得。粘着剂例如为环氧树脂与丙烯酸酯树 脂。填隙物可例如塑胶、玻璃珠、或某些砂粉。间隙胶14的厚度(即透明导 电层13与17之间的距离)介于10μm至300μm之间。若透明导电层之间的距离 过小，则有漏电及变色不均匀的现象。若透明导电层之间的距离过大，则反 应速度变慢。上述光调变装置在不通电时，其光调变组合物原本的中性态为 透明。藉由施加正电压至光调变装置，其颜色将逐渐转深。一旦关闭电源， 则光调变组合物在短时间内(小于1秒)即恢复为原本的透明状态。由实验结果 可知，上述光调变装置的透明/深色之间的开关循环可重复超过10000次，即 光调变组合物具有良好的稳定性。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂，下文特 举多个实施例并配合所附图示，作详细说明如下：
实施例
以下实施例所提及的测量仪器及方法：下列实施例的循环伏安法(cyclicvoltammetry，CV)系使用三电极系统进行测量，其中以ITO玻璃作为工作电 极(面积约为3.0cm×2.0cm)，而参考电极(reference electrode)为自制的 Ag/AgCl(饱和KCl)电极，辅助电极(auxiliary electrode)为白金丝或白金网， 电解液为0.1M的四丁基过氯酸铵的乙腈溶液，且扫描速率为50mV/s。其中 氧化还原电位的平均值定义为材料的半波电位。
实施例A1(双异丁基酰胺三苯胺的制备)
取10.0克4-甲氧基三苯胺二胺(MeOTPA-diNH2)与6.40克异丁酸置于反 应瓶中混合。取25mL二甲基乙酰胺(DMAc)作为溶剂加入反应瓶后，再取20.3 克磷酸三苯酯(TPP)及5.68克吡啶作为催化剂加入反应瓶。将反应瓶中的混合 物加热至105℃反应4小时后冷却至室温，再将反应结果倒入乙醇中析出固 体。收集固体后冲洗烘干，即得白色产物。上述反应如式7所示，且产物的 光谱如下：1H NMR(500MHz,DMSO-d6)：δ1.02(d,J＝7.0Hz,6H),2.49(m, 2H),3.66(s,3H),6.78(d,J＝9.0Hz,4H),6.81(d,J＝8.5Hz,2H),6.87(d,J＝ 8.5Hz,2H),7.41(d,J＝9.0Hz,4H),9.65(s,2H).13C NMR(125MHz, DMSO-d6)：δ19.5,34.8,55.2,114.8,120.4,122.9,125.7,133.9,140.5,143.0, 155.2,174.8.Anal.calcd forC27H31N3O3：C,72.78；H,7.01；N,9.43；found： C,72.69；H,7.03；N,9.51。上述产物的循环伏安谱如图2所示，氧化还原电 位如表1所示，中性态与氧化态的穿透光谱如图4所示，而中性态与氧化态于 不同波长的穿透度如表2所示。
实施例A2(双环己烷基酰胺三苯胺的制备)
取10.0克MeOTPA-diNH2与8.40克环己酸置于反应瓶中混合。取25mL DMAc作为溶剂加入反应瓶中，并取20.3克TPP及5.68克吡啶作为催化剂加入 反应瓶。将反应瓶中的混合物加热至105℃反应4小时后冷却至室温，再将反 应结果倒入乙醇中析出固体。收集固体后冲洗烘干，即得白色产物。上述反 应如式8所示，且产物的光谱如下：1H NMR(500MHz,DMSO-d6)：δ1.13～1.44 (m,10H),1.63～1.79(m,10H),2.29(t,2H),3.72(s,3H),6.84(d,J＝9.0Hz,4H), 6.88(d,J＝8.5Hz,2H),6.95(d,J＝8.5Hz,2H),7.48(d,J＝9.0Hz,4H),9.67(s, 2H).13C NMR(125MHz,DMSO-d6)：δ13.9,22.0,25.1,28.5,28.6,31.2,55.2, 114.8,120.2,122.8,125.8,140.5,143.0,155.24,170.8.Anal.calcd for C33H39N3O3：C,75.4；H,7.48；N,7.99；found：C,74.8；H,7.45；N,7.87。 上述产物的氧化还原电位如表1所示，而中性态与氧化态于不同波长的穿透 度如表2所示。
实施例A3(双庚烷基酰胺三苯胺的制备)
取10.0克MeOTPA-diNH2与9.45克辛酸置于反应瓶中混合。取25mL DMAc作为溶剂加入反应瓶中，并取20.3克TPP及5.68克吡啶作为催化剂加入 反应瓶。将反应瓶中的混合物加热至105℃反应4小时后冷却至室温，再将反 应结果倒入乙醇中析出固体。收集固体后冲洗烘干，即得白色产物。上述反 应如式9所示，且产物的光谱如下：1H NMR(500MHz,DMSO-d6)：δ0.86(t, 6H),1.26～1.59(m,16H),2.51(t,4H),3.73(s,3H),6.85(d,J＝9.0Hz,4H),6.88 (d,J＝8.5Hz,2H),6.95(d,J＝8.5Hz,2H),7.47(d,J＝9.0Hz,4H),9.76(s,2H). 13CNMR(125MHz,DMSO-d6)：δ13.9,22.0,25.2,28.5,28.6,31.2,55.2,114.8, 120.2,122.8,125.8,133.8,140.5,143.0,155.2,170.8.Anal.calcd for C33H43N3O3：C,74.82；H,8.18；N,7.93；found：C,74.89；H,8.09；N,7.88。 上述产物的氧化还原电位如表1所示，而中性态与氧化态于不同波长的穿透 度如表2所示。
实施例A4(双环己烷基酰胺五苯二胺的制备)
取10.0克4-甲氧基五苯二胺(MeOTPPA-diNH2)与5.1克环己酸置于反应 瓶中混合。取25mL DMAc作为溶剂加入反应瓶中，并取20.3克TPP及5.68克 吡啶作为催化剂加入反应瓶。将反应瓶中的混合物加热至105℃反应4小时后 冷却至室温，再将反应结果倒入乙醇中析出固体。收集固体后冲洗烘干，即 得白色产物。上述反应如式10所示，且产物的光谱如下：1H NMR(500MHz, DMSO-d6)：δ1.24～1.38(m,10H),1.40～1.75(m,10H),1.77(t,2H),3.72(s,6H), 6.79(s,4H),6.87～6.88(m,6H),6.97(d,J＝8.5Hz,2H),7.47(d,J＝9.0Hz,4H), 9.69(s,2H).13C NMR(125MHz,DMSO-d6)：δ25.2,25.4,29.1,44.7,55.2, 114.8,120.3,123.0,123.2,125.9,134.0,140.4,142.0,142.9,155.3,173.8.Anal. calcd forC46H52N4O4：C,76.21；H,7.23；N,7.73；found：C,75.95；H,7.29； N,7.75。上述产物的循环伏安谱如图3所示，氧化还原电位如表1所示，中性 态与氧化态的穿透光谱如图5所示，而中性态与氧化态于不同波长的穿透度 如表2所示。
实施例B1(双环己烷酰亚胺三苯胺的制备)
取1.50克MeOTPA-diNH2与1.70克六氢苯酐(HHPA)置于反应瓶中混合。 取2.5mLDMAc作为溶剂加入反应瓶中，并取少量异喹啉作为催化剂加入反 应瓶。将反应瓶中的混合物加热至210℃反应5小时后冷却至室温，以甲醇稀 释反应结果后将其倒入水中析出固体。收集固体后冲洗烘干，即得米白色产 物。上述反应如式11所示，且产物的光谱如下：1H NMR(500MHz,DMSO-d6)： δ1.38(m,4H),1.73(q,4H),3.08(q,2H),3.75(s,3H),6.97(d,J＝9.5Hz,2H), 7.02(d,J＝9.0Hz,4H),7.11(d,J＝9.5Hz,2H),7.14(d,J＝9.0Hz,4H).13C NMR(125MHz,DMSO-d6)：δ21.4,23.4,55.3,115.4,122.0,126.2,127.9,128.1, 139.1,147.0,156.7,178.8.Anal.calcd for C35H35N3O5：C,72.77；H,6.11；N, 7.27；found：C,72.35；H,6.16；N,7.25。上述产物的循环伏安谱如图2所示， 氧化还原电位如表1所示，氧化态的穿透光谱如图4所示，而中性态与氧化态 于不同波长的穿透度如表2所示。
实施例B2(双环己烷酰亚胺五苯二胺的制备)
取5.0克MeOTPPA-diNH2与3.06克HHPA置于反应瓶中混合。取7.5mL DMAc作为溶剂加入反应瓶中，并取少量异喹啉作为催化剂加入反应瓶。将 反应瓶中的混合物加热至210℃反应5小时后冷却至室温，以甲醇稀释反结果 后将其倒入水中析出固体。收集固体后冲洗烘干，即得米白色产物。上述反 应如式12所示，且产物的光谱如下：1H NMR(500MHz,DMSO-d6)：δ 1.36～1.42(m,8H),1.70～2.00(m,8H),3.08(t,4H),3.74(s,6H),6.92～7.10(m, 20H).13C NMR(125MHz,DMSO-d6)：δ21.3,21.4,23.3,55.2,115.2,120.2, 124.9,125.0,127.5,127.7,139.4,142.2,147.6,156.3,178.8.Anal.calcd for C48H46N4O6：C,74.40；H,5.98；N,7.23；found：C,74.21；H,6.03；N,7.27。 上述产物的循环伏安谱如图3所示，氧化还原电位如表1所示，中性态与氧化 态的穿透光谱如图5所示，而中性态与氧化态于不同波长的穿透度如表2所 示。
表1
| 实施例 | E<sup>1</sup><sub>1/2</sub>(V) | E<sup>2</sup><sub>1/2</sub>(V) |
| A1 | 0.68(蓝绿色) | - |
| A2 | 0.67(蓝绿色) | - |
| A3 | 0.68(蓝绿色) | - |
| A4 | 0.46(绿色) | 0.81(蓝色) |
| B1 | 0.93(蓝色) | - |
| B2 | 0.60(绿色) | 0.94(蓝色) |
*注：E1 1/2代表第一段氧化半波电位；E2 1/2代表第二段氧化半波电位
由表1及图1与2可知，三苯胺系统(实施例A1至A3与B1)仅具一段氧化还 原峰，而五苯二胺系统(实施例A4与B2)具有两段的氧化还原峰。末端为酰胺 基团(amido)及酰亚胺基(imido)的电位值差异极大(A1vs.B1，及A4vs.B2)。 藉由末端官能基不同，可调控光调变化合物的氧化还原电位。
表2
*PSN为吩噻嗪(phenothiazine)
由表2及图3与4可知，三苯胺化合物A1及B1在可见光区遮蔽效果都优于 比较例PSN，且五苯二胺化合物不仅可吸收可见光区，在NIR区段的热辐射 吸收效果尤佳。简言之，五苯二胺化合物具有防紫外线及NIR吸收的特性。
实施例C1(光调变装置的制备)
将四丁基四氟硼酸铵(TBABF4)溶于碳酸丙烯酯(PC)中，形成0.5M溶液。 将实施例A2的产物与紫精[(HV(BF4)2]溶于上述溶液形成光调变组合物溶液， 其中实施例A2的产物浓度为0.1M，紫精浓度为0.05M。裁切两片适宜大小的 ITO导电玻璃，以间隙胶限定ITO导电玻璃之间的间距(50μm)后，将前述配 制好的光调变组合物溶液灌入ITO导电玻璃之间的空间，封口后即得光调变 装置。对上述光调变装置施加1.4V的工作电压，用来测量光谱电化学法系以 Agilent 8453 UV-Vis光谱仪同步侦测样品的UV-Vis-NIR光谱，其对不同波长的穿透度如表3所示。
实施例C2(光调变装置的制备)
将TBABF4溶于PC中，形成0.5M溶液。将实施例B1的产物与紫精 [(HV(BF4)2]溶于上述溶液形成光调变组合物溶液，其中实施例B1的产物浓度 为0.1M，紫精浓度为0.05M。裁切两片适宜大小的ITO导电玻璃，以间隙胶 限定ITO导电玻璃之间的间距(50μm)后，将前述配制好的光调变组合物溶液 灌入ITO导电玻璃之间的空间，封口后即得光调变装置。对上述光调变装置 施加1.6V工作电压，测量其对不同波长的穿透度如表3所示。上述装置的中 性态(关闭态)与氧化态(开启态)的穿透光谱如图6所示。
实施例C3(光调变装置的制备)
将TBABF4溶于PC中，形成0.5M溶液。将实施例A4的产物与紫精 [(HV(BF4)2]溶于上述溶液形成光调变组合物溶液，其中实施例A4的产物浓度 为0.1M，紫精浓度为0.05M。裁切两片适宜大小的ITO导电玻璃，以间隙胶 限定ITO导电玻璃之间的间距(50μm)后，将前述配制好的光调变组合物溶液 灌入ITO导电玻璃之间的空间，封口后即得光调变装置。对上述光调变装置 施加1.1V工作电压，测量其对不同波长的穿透度如表3所示。
实施例C4(光调变装置的制备)
将TBABF4溶于碳酸丙烯酯(PC)中，形成0.5M溶液。将实施例B2的产物 与紫精[(HV(BF4)2]溶于上述溶液形成光调变组合物溶液，其中实施例B2的产 物浓度为0.1M，紫精浓度为0.05M。裁切两片适宜大小的ITO导电玻璃，以 间隙胶限定ITO导电玻璃之间的间距(50μm)后，将前述配制好的光调变组合 物溶液灌入ITO导电玻璃之间的空间，封口后即得光调变装置。对上述光调 变装置施加1.3V工作电压，测量其对不同波长的穿透度如表3所示。
表3
由表3及图6可知，加入紫精后的实施例均可看出于波长600nm附近增加 遮蔽的效果。实施例C3及C4的五苯二胺系统在波长400～500nm的遮蔽率，皆 大于实施例C1及C2。与比较例H相比较，所有实施例在波长350～800nm的遮 蔽率都较高，因为三苯胺或五苯二胺系统在氧化还原状态的共轭性较佳。
实施例D(光调变装置的寿命测量)
将TBABF4溶于碳酸丙烯酯(PC)中，形成0.5M溶液。将实施例A1的产物 与紫精[(HV(BF4)2]溶于上述溶液形成光调变组合物溶液，其中实施例A1的产 物浓度为0.1M，紫精浓度为0.05M。裁切两片适宜大小的ITO导电玻璃，以 间隙胶定义ITO导电玻璃之间的间距(50μm)后，将前述配制好的光调变组合 物溶液灌入ITO导电玻璃之间的空间，封口后即得光调变装置。
对上述光调变装置施加正向电压1.30V(开启状态)持续3.250秒后，提供 负电压-1.30V持续0.375秒(关闭状态)，最后零电位0V(原本中性态)停留3.675 秒。重复上述循环进行循环寿命测试，由穿透光谱(见图7)可见，原本中性态 时可见光区完全无吸收，转变成氧化态时可见光区的绿光及红光区被吸收 (装置呈蓝色)。此外，上述光调变装置的开/关循环次数在超过10000次后仍 具有类似的开/关状态的穿透图谱，证明其稳定性。上述光调变装置于不同状 态对不同波长的光穿透度如表4所示。
表4
实施例E(透明-绿色的光调变互补式元件的制备)
将TBABF4溶于PC中，形成0.5M溶液。将实施例A1的产物、5,10-二甲 基吩嗪(DMP)、与紫精[(HV(BF4)2]溶于上述溶液形成光调变组合物溶液，其 中实施例A1的产物浓度为0.025M、DMP浓度为0.025M、且紫精浓度为 0.05M。裁切两片适宜大小的ITO导电玻璃，以间隙胶限定ITO导电玻璃之间 的间距(50μm)后，将前述配制好的光调变组合物溶液灌入ITO导电玻璃之间 的空间，封口后即得光调变装置。
对上述光调变装置施加正向电压慢慢增加至1.3V，由光谱可见装置对波 长450nm的光穿透度降低至10.4％。至于装置外观则由透明的中性态慢慢转 变成墨绿色的开启态。之后移开正向电压，光调变装置在1秒内回复为透明 的中性态(关闭态)。
实施例F(透明-深蓝色的光调变互补式元件的制备)
将TBABF4溶于PC中，形成0.5M溶液。将实施例A1的产物、吩噻嗪(PSN)、 N-甲基吩噻嗪(MePSN)、与紫精[(HV(BF4)2]溶于上述溶液形成光调变组合物 溶液，其中实施例A1的产物浓度为0.05M、PSN浓度为0.05M、MePSN浓度 为0.05M，且紫精浓度为0.05M。裁切两片适宜大小的ITO导电玻璃，以间隙 胶定义ITO导电玻璃之间的间距(50μm)后，将前述配制好的光调变组合物溶 液灌入ITO导电玻璃之间的空间，封口后即得光调变装置。
对上述光调变装置施加正向电压慢慢增加至1.5V，由光谱可见装置对波 长450nm的光穿透度降低至10.4％。至于装置外观则由透明的中性态慢慢转 变成深蓝色的开启态。之后移开正向电压，光调变装置在1秒内回复为透明 的中性态(关闭态)。
实施例G(透明-黑色的光调变互补式元件的制备)
将TBABF4溶于PC中，形成0.5M溶液。将实施例A1的产物、PSN、N- 甲基吩噻嗪(MePSN)、与紫精[(HV(BF4)2]溶于上述溶液形成光调变组合物溶 液，其中实施例A1的产物浓度为0.1M、PSN浓度为0.1M、MePSN浓度为0.1M， 且紫精浓度为0.1M。裁切两片适宜大小的ITO导电玻璃，以间隙胶定义ITO 导电玻璃之间的间距(50μm)后，将前述配制好的光调变组合物溶液灌入ITO 导电玻璃之间的空间，封口后即得光调变装置。
对上述光调变装置施加正向电压慢慢增加至1.5V，由光谱可知，可见波 长450nm的光穿透度在电压1.2V时达9.8％，在电压达1.5V时光学穿透度达 1.8％。至于装置外观则由透明的中性态慢慢转变成黑色的开启态。上述装置 在不同电压下的光穿透度图谱如图8所示。之后移开正向电压，光调变装置 在1秒内回复为透明的中性态(关闭态)。
比较例H(光调变装置的制备)
将TBABF4溶于PC中，形成0.5M溶液。将PSN与紫精[(HV(BF4)2]溶于上 述溶液形成光调变组合物溶液，其中PSN浓度为0.1M，紫精浓度为0.05M。 裁切两片适宜大小的ITO导电玻璃，以间隙胶限定ITO导电玻璃之间的间距 (50μm)后，将前述配制好的光调变组合物溶液灌入ITO导电玻璃之间的空间， 封口后即得光调变装置。上述光调变组合物的氧化态的穿透光谱如图4所示， 而中性态与氧化态的穿透度如表2所示。
对上述光调变装置施加正向电压慢慢增加至1.3V，装置外观由淡蓝色的 中性态慢慢转变成深蓝色的开启态。测量上述光调变装置对不同波长的穿透 度如表3所示。上述光调变装置的中性态与氧化态(开启态)的穿透图谱如图6 所示。
虽然本公开以数个实施例揭露如上，然其并非用以限定本发明，任何本 技术领域的技术人员，在不脱离本公开的精神和范围内，当可作任意的更动 与润饰，因此本公开的保护范围应以所附权利要求书所界定的范围为准。
Claims (10)
1.一种有机化合物，其结构为：
其中R4为H，R5为异丙基或环己基，其中R6为环己基。
2.一种光调变组合物，包括：
第一可氧化化合物，为权利要求1所述的有机化合物；
可还原化合物；
电解质；以及
溶剂。
3.如权利要求2所述的光调变组合物，其中该电解质为有机铵盐或无机锂盐。
4.如权利要求2所述的光调变组合物，其中该第一可氧化化合物与该电解质的摩尔比例为1:1至1:20，而可还原化合物与该电解质的摩尔比例为1:1至1:20。
5.如权利要求2所述的光调变组合物，其中该电解质的浓度为0.01M至1.5M。
6.如权利要求2所述的光调变组合物，其中该可还原化合物为或上述的组合，其中R7为C1-10烷基。
7.如权利要求2所述的光调变组合物，还包括第二可氧化化合物，其中该第二可氧化化合物的结构为：
或上述的组合，其中R8为H或烷基。
8.一种光调变装置，包括：
对电极，其包括：
第一透明基板，其一表面具有透明导电层；以及
第二透明基板，其一表面具有透明导电层，该第二透明导电层相对组立；
间隙胶，该间隙胶接合于该对电极具有透明导电层的一侧面间，且该对电极与该间隙环间形成密闭空间；以及
填入该密闭空间的光调变组合物，其中该光调变组合物包括：
第一可氧化化合物，为权利要求1所述的有机化合物；
可还原化合物；
电解质；以及
溶剂。
9.如权利要求8所述的光调变装置，其中该光调变组合物还包括第二可氧化化合物，其中该第二可氧化化合物的结构为：
或上述的组合，其中R8为H或烷基。
10.如权利要求8所述的光调变装置，其中该第一透明导电层与该第二透明导电层之间的距离为10μm至300μm。
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| Publication number | Publication date |
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| TW201718463A (zh) | 2017-06-01 |
| US20170146881A1 (en) | 2017-05-25 |
| CN106748868A (zh) | 2017-05-31 |
| TWI551574B (zh) | 2016-10-01 |
| JP6234427B2 (ja) | 2017-11-22 |
| US10007164B2 (en) | 2018-06-26 |
| JP2017095435A (ja) | 2017-06-01 |
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