CN110724163B - 一种5-甲基吡啶四氮唑四核铜[i]配合物在刺激响应发光变色材料的应用 - Google Patents
一种5-甲基吡啶四氮唑四核铜[i]配合物在刺激响应发光变色材料的应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 31
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- -1 5-methylpyridine tetrazole Chemical class 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 18
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000575 pesticide Substances 0.000 claims abstract description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 6
- ITQTTZVARXURQS-UHFFFAOYSA-N beta-methylpyridine Natural products CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
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- 239000013078 crystal Substances 0.000 claims description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- 238000003701 mechanical milling Methods 0.000 claims 1
- 230000000638 stimulation Effects 0.000 abstract description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000843 powder Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 150000003536 tetrazoles Chemical class 0.000 description 10
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- 238000000034 method Methods 0.000 description 9
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- 239000012046 mixed solvent Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
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- 238000000227 grinding Methods 0.000 description 6
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- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
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- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 229910052802 copper Inorganic materials 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- 125000003831 tetrazolyl group Chemical group 0.000 description 3
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- 235000010290 biphenyl Nutrition 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
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- 229910052762 osmium Inorganic materials 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- QATLRIDVUPPCGT-UHFFFAOYSA-N pyridine;2h-tetrazole Chemical compound C1=NN=NN1.C1=CC=NC=C1 QATLRIDVUPPCGT-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- GCWJZPIYCFBBHX-UHFFFAOYSA-N 5-methyl-2-(2h-tetrazol-5-yl)pyridine Chemical compound N1=CC(C)=CC=C1C1=NNN=N1 GCWJZPIYCFBBHX-UHFFFAOYSA-N 0.000 description 1
- AVYXASMIUOIQII-UHFFFAOYSA-N [(diphenylphosphanylamino)-phenylphosphanyl]benzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)NP(C=1C=CC=CC=1)C1=CC=CC=C1 AVYXASMIUOIQII-UHFFFAOYSA-N 0.000 description 1
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明提供了一种5‑甲基吡啶四氮唑四核铜[I]配合物在刺激响应发光变色材料的应用,所述5‑甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料为高氯酸根·二[5‑[5‑甲基‑2‑吡啶基]四氮唑基]·四[N,N‑双[二苯基磷酰]胺]合四铜[I]配合物,其分子式为:C110H96Cl2Cu4N14O8P8,还包括了该配合物的分子结构。其属于一种刺激响应发光变色的新材料,具有良好的应用前景。
Description
技术领域
本发明涉及一种5-甲基吡啶四氮唑四核铜[I]配合物在刺激响应发光变色材料的应用,属于刺激响应发光变色新材料合成技术领域。
背景技术
目前,由于受强自旋轨道耦合作用和重原子效应的影响,金属发光配合物理论上可利用所有的单重态和三重态能量,提升发光量子效率。当前,金属发光配合物的研究主要集中于第五、六周期的过渡金属,尤其是第VIII族的过渡金属,如钌、锇、铱、铂。然而,第五、六周期的过渡金属(除第一、二副族的少数几种金属外)在地壳中均含量稀少,开采困难,因此,基于此类贵金属所制得的发光材料的使用成本较高,而且大规模使用后还会带来原材料来源紧张的问题。此外,此类贵金属的化合物通常有较大毒性,尤其是钌、锇、铼等金属化合物。因而,基于此类贵金属化合物的发光材料在大规模使用后还会带来环境污染及给生产和使用者带来直接或间接伤害。高使用成本及对环境不友好等缺点使得它们的大规模应用受到极大限制,因此人们特别期望能够在第五、六周期之外找寻到其它可替代的金属元素。
相较于第五、六周期的过渡金属,位于第四周期的金属铜,不仅资源丰富,价格低廉,而且发光优良,性能独特,环境友好。此外,一价铜配合物还具有良好的室温可见磷光发射,其光色可在紫外至近红外区变化,涵盖整个的可见光区。资源丰富、价格低廉、发光优良,性能独特、环境友好等诸多优点使得一价铜发光配合物在发光器件、智能材料、光学传感、非线性光学、光伏器件等诸多领域中表现出良好的应用前景。
目前,文献资料中公开报道的一价铜发光配合物主要有一价铜单核配合物和多核簇合物。一价铜多核簇合物因其结构新颖,构型丰富,配位多样,发光独特等优点,近年来越来越受到人们的关注。然而,应用氮杂环多齿配体和有机双膦配体,构建基于一价铜配合物的发光变色材料的文献报道却很少,尤其是基于一价铜配合物的刺激响应发光变色材料。
应用5-甲基吡啶四氮唑多齿配体[5-[5-甲基-2-吡啶基]四氮唑]和有机双膦配体[N,N-双[二苯基磷酰]胺],设计合成一价铜配合物,并运用于刺激响应发光变色材料,目前尚未见文献公开报道。
发明内容
本发明的目的在于克服现有技术之缺陷,提供了一种5-甲基吡啶四氮唑四核铜[I]配合物在刺激响应发光变色材料的应用,其属于一种刺激响应发光变色的新材料。
本发明是这样实现的:
本发明提供一种5-甲基吡啶四氮唑四核铜[I]配合物在刺激响应发光变色材料的应用,所述5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料为高氯酸根·二[5-[5-甲基-2-吡啶基]四氮唑基]·四[N,N-双[二苯基磷酰]胺]合四铜[I]配合物,其分子式为:C110H96Cl2Cu4N14O8P8,分子结构为:
进一步地,所述高氯酸根·二[5-[5-甲基-2-吡啶基]四氮唑基]·四[N,N-双[二苯基磷酰]胺]合四铜[I]配合物晶体属三斜晶系,P-1空间群,晶胞参数:a=13.539(3),b=16.925(3),α=97.602(5)°,β=92.874(5)°,γ=110.675(5)°,Mr=3045.78,Z=1,Dc=1.338g cm-3,μ=0.744mm-1,GOF=1.023。
本发明还提供两种制备方法:
制备5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料的方法之一:
在氩气气氛下,摩尔比为2:2:1的[Cu[CH3CN]4][ClO4]、N,N-双[二苯基磷酰]胺[简称dppa]、5-[5-甲基-2-吡啶基]四氮唑[简称5-mpytzH]在二氯甲烷中常温搅拌反应2-4小时,后往该反应液中加入与5-[5-甲基-2-吡啶基]四氮唑配体等摩尔量的氢氧化钠,并继续常温搅拌反应1-2小时,后用旋转蒸发仪将溶剂减压蒸干,用N,N-二甲基甲酰胺[简称DMF]-乙醚混合溶剂[体积比为1:10]进行重结晶,过滤重结晶得到的淡黄色晶态产物,用乙醚洗涤3-4次,真空干燥后得到淡黄色固体产物。
制备5-甲基吡啶四氮唑四核铜[I]配合物机刺激响应发光变色材料的方法之二:
在氩气气氛下,摩尔比为1:5-10:2:1的六水高氯酸铜[Cu[ClO4]2·6H2O]、过量铜粉、N,N-双[二苯基磷酰]胺[简称dppa]、5-[5-甲基-2-吡啶基]四氮唑[简称5-mpytzH]在乙腈-二氯甲烷混合溶剂[体积比为1:2]中常温搅拌反应2-4小时,后往该反应液中加入与5-[5-甲基-2-吡啶基]四氮唑配体等摩尔量的氢氧化钠,并继续常温搅拌反应1-2小时,过滤后用旋转蒸发仪将溶剂减压蒸干,用N,N-二甲基甲酰胺[简称DMF]-乙醚混合溶剂[体积比为1:10]进行重结晶,过滤重结晶得到的淡黄色晶态产物,用乙醚洗涤3-4次,真空干燥后得到淡黄色固体产物。
本发明具有以下有益效果:
本发明的5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料中在吡啶环5号位上引入甲基和选用N,N-双[二苯基磷酰]胺的主要目的和意义:在具有螯合和桥联功能的吡啶四氮唑多齿配体的吡啶环5号位上引入具有合适空间大小和给电子性质的甲基和选用具有桥联功能的N,N-双[二苯基磷酰]胺,主要用于调控铜[I]配合物的空间立体效应、电子密度分布和分子内π-π作用,实现铜[I]配合物完全可逆的刺激响应发光变色性质。在常温下,该铜[I]配合物固体颗粒的发光波长最大值为477nm,发光寿命为16μs,发光量子效率为13%。当该固体颗粒被研磨后,其固体粉末的发光波长最大值变为501nm,发光寿命为22μs,发光量子效率为18%,而当该研磨后的固体粉末放置于二氯甲烷蒸汽气氛中后,其发光波长最大值变为469nm,发光寿命为16μs,发光量子效率为11%;当该固体粉末再次被研磨后,其发光波长最大值重新变为501nm,而当该研磨后的固体粉末再次放置于二氯甲烷蒸汽气氛中后,其发光波长最大值也重新变为469nm;周而复始,不断循环。研究结果表明本发明的5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料,在机械研磨作用下会产生发光变色性质,而在二氯甲烷蒸汽下又能恢复原来的发光,即本发明的铜[I]配合物固体对于机械研磨和二氯甲烷蒸汽均具有刺激响应特性,可用于制作能感应和检测机械研磨作用和二氯甲烷蒸汽的元器件。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。
图1为本发明实施例提供的高氯酸根·二[5-[5-甲基-2-吡啶基]四氮唑基]·四[N,N-双[二苯基磷酰]胺]合四铜[I]配合物晶体结构图。
图2为本发明实施例提供的高氯酸根·二[5-[5-甲基-2-吡啶基]四氮唑基]·四[N,N-双[二苯基磷酰]胺]合四铜[I]配合物固态荧光发射光谱图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
如图1和图2,本发明提供一种5-甲基吡啶四氮唑四核铜[I]配合物在刺激响应发光变色材料的应用,所述5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料为高氯酸根·二[5-[5-甲基-2-吡啶基]四氮唑基]·四[N,N-双[二苯基磷酰]胺]合四铜[I]配合物,其分子式为:C110H96Cl2Cu4N14O8P8,分子结构为:
本发明还提供两种制备方法:
制备5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料的方法之一:
在氩气气氛下,摩尔比为2:2:1的[Cu[CH3CN]4][ClO4]、N,N-双[二苯基磷酰]胺[简称dppa]、5-[5-甲基-2-吡啶基]四氮唑[简称5-mpytzH]在二氯甲烷中常温搅拌反应2-4小时,后往该反应液中加入与5-[5-甲基-2-吡啶基]四氮唑配体等摩尔量的氢氧化钠,并继续常温搅拌反应1-2小时,后用旋转蒸发仪将溶剂减压蒸干,用N,N-二甲基甲酰胺[简称DMF]-乙醚混合溶剂[体积比为1:10]进行重结晶,过滤重结晶得到的淡黄色晶态产物,用乙醚洗涤3-4次,真空干燥后得到淡黄色固体产物。
制备5-甲基吡啶四氮唑四核铜[I]配合物机刺激响应发光变色材料的方法之二:
在氩气气氛下,摩尔比为1:5-10:2:1的六水高氯酸铜[Cu[ClO4]2·6H2O]、过量铜粉、N,N-双[二苯基磷酰]胺[简称dppa]、5-[5-甲基-2-吡啶基]四氮唑[简称5-mpytzH]在乙腈-二氯甲烷混合溶剂[体积比为1:2]中常温搅拌反应2-4小时,后往该反应液中加入与5-[5-甲基-2-吡啶基]四氮唑配体等摩尔量的氢氧化钠,并继续常温搅拌反应1-2小时,过滤后用旋转蒸发仪将溶剂减压蒸干,用N,N-二甲基甲酰胺[简称DMF]-乙醚混合溶剂[体积比为1:10]进行重结晶,过滤重结晶得到的淡黄色晶态产物,用乙醚洗涤3-4次,真空干燥后得到淡黄色固体产物。
本发明采用的反应机理如下:
上述制备方法所得的5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料的物性参数如下:
分子式:C110H96Cl2Cu4N14O8P8;
分子量:2314.9;
中文名称:高氯酸根·二[5-[5-甲基-2-吡啶基]四氮唑基]·四[N,N-双[二苯基磷酰]胺]合四铜[I]配合物;
英文名称:[Cu4[5-(5-methyl-2-pyridyl)tetrazolate]2[N,N-bis(diphenylphosphino)amine]4][ClO4]2,简写为:[Cu4[5-mpytz]2[dppa]4][ClO4]2。
以下通过两个具体的实施例进行说明:
实施例1
在氩气气氛下,[Cu[CH3CN]4][ClO4](29.4mg,0.090mmol)、N,N-双[二苯基磷酰]胺(34.7mg,0.090mmol)和5-[5-甲基-2-吡啶基]四氮唑(7.3mg,0.045mmol)在10mL二氯甲烷中常温搅拌反应3小时,后往该反应液中加入氢氧化钠(1.8mg,0.045mmol),常温下继续搅拌反应1小时,后用旋转蒸发仪将溶剂减压蒸干,用N,N-二甲基甲酰胺(1mL)-乙醚(10mL)混合溶剂[体积比为1:10]进行重结晶。过滤重结晶得到的淡黄色晶态产物,用10mL乙醚洗涤3-4次,真空干燥后得到淡黄色固体产物(37.1mg,0.016mmol),产率为71%。
元素分析计算值(C110H96Cl2Cu4N14O8P8)为(%):C 57.07,H 4.18,N 8.47;实测值:C57.09,H 4.19,N 8.45.
X-射线单晶衍射:晶体属三斜晶系,P-1空间群,晶胞参数:a=13.539(3),b=16.925(3),α=97.602(5)°,β=92.874(5)°,γ=110.675(5)°,Mr=3045.78,Z=1,Dc=1.338g cm-3,μ=0.744mm-1,GOF=1.023,晶体结构图如图1所示。
光致发光性能测试结果表明,该四核铜[I]配合物固体在常温下表现出可逆的刺激响应发光变色性能。在常温下,该铜[I]配合物固体颗粒的发光波长最大值为477nm,发光寿命为16μs,发光量子效率为13%。当该固体颗粒被研磨后,其固体粉末的发光波长最大值变为501nm,发光寿命为22μs,发光量子效率为18%,而当该研磨后的固体粉末放置于二氯甲烷蒸汽气氛中后,其发光波长最大值变为469nm,发光寿命为16μs,发光量子效率为11%;当该固体粉末再次被研磨后,其发光波长最大值重新变为501nm,而当该研磨后的固体粉末再次放置于二氯甲烷蒸汽气氛中后,其发光波长最大值也重新变为469nm;周而复始,不断循环。其固态荧光发射光谱如图2所示。
实施例2
在氩气气氛下,六水高氯酸铜[Cu[ClO4]2·6H2O](15.6mg,0.042mmol)和过量铜粉(16.5mg,0.260mmol)在5mL乙腈中常温搅拌反应30分钟,后加入N,N-双[二苯基磷酰]胺(32.4mg,0.084mmol)的10mL二氯甲烷溶液,继续搅拌反应1小时后加入5-[5-甲基-2-吡啶基]四氮唑配体(6.8mg,0.042mmol),常温下继续搅拌反应2小时,后往该反应液中加入氢氧化钠(1.7mg,0.042mmol),并继续常温搅拌反应1小时,过滤后用旋转蒸发仪将溶剂减压蒸干,用N,N-二甲基甲酰胺(1mL)-乙醚(10mL)混合溶剂[体积比为1:10]进行重结晶。过滤重结晶得到的淡黄色晶态产物,用10mL乙醚洗涤3-4次,真空干燥后得到淡黄色固体产物(32.6mg,0.014mmol),产率为67%。
分析表征实验数据同实施例1。
本发明的5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料中在吡啶环5号位上引入甲基和选用N,N-双[二苯基磷酰]胺的主要目的和意义:在具有螯合和桥联功能的吡啶四氮唑多齿配体的吡啶环5号位上引入具有合适空间大小和给电子性质的甲基和选用具有桥联功能的N,N-双[二苯基磷酰]胺,主要用于调控铜[I]配合物的空间立体效应、电子密度分布和分子内π-π作用,实现铜[I]配合物完全可逆的刺激响应发光变色性质。在常温下,该铜[I]配合物固体颗粒的发光波长最大值为477nm,发光寿命为16μs,发光量子效率为13%。当该固体颗粒被研磨后,其固体粉末的发光波长最大值变为501nm,发光寿命为22μs,发光量子效率为18%,而当该研磨后的固体粉末放置于二氯甲烷蒸汽气氛中后,其发光波长最大值变为469nm,发光寿命为16μs,发光量子效率为11%;当该固体粉末再次被研磨后,其发光波长最大值重新变为501nm,而当该研磨后的固体粉末再次放置于二氯甲烷蒸汽气氛中后,其发光波长最大值也重新变为469nm;周而复始,不断循环。
研究结果表明本发明的5-甲基吡啶四氮唑四核铜[I]配合物刺激响应发光变色材料,在机械研磨作用下会产生发光变色性质,而在二氯甲烷蒸汽下又能恢复原来的发光,即本发明的铜[I]配合物固体对于机械研磨和二氯甲烷蒸汽均具有刺激响应特性,可用于制作能感应和检测机械研磨作用和二氯甲烷蒸汽的元器件;其属于一种刺激响应发光变色的新材料。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
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