CN110386930B - 聚集诱导发光化合物、其制备方法及其应用 - Google Patents
聚集诱导发光化合物、其制备方法及其应用 Download PDFInfo
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Abstract
Description
技术领域
本发明涉及功能材料领域,特别是涉及一种聚集诱导发光化合物、其制备方法及其应用,例如具有深红/近红外固体发射特性的化合物、其制备方法以及其在有机电致发光器件(例如有机电致发光二极管OLED)和/或生物医学(例如非诊断目的的生物成像,如生物荧光探针)中的应用。
背景技术
高端光电子器件的发展促使了具有深红/近红外发射(650-900nm)的荧光材料的快速发展。在光电器件中,深红/近红外发光材料是构造全彩色和近红外有机发光二极管(OLED)的重要组成部分。特别是近红外发射的OLED在光通信、夜视设备和信息安全显示中具有重要的意义。然而,长发射波长与高发光量子产率(PLQY)之间的内在矛盾给高效深红/近红外发光材料的发展带来了巨大的挑战。近年来,人们致力于开发具有深红/近红外发射的高效发光材料,包括过渡金属配合物(如Pt2+、Os3+或Ir3+)、镧系配合物、有机小分子和共轭聚合物。然而,金属配合物往往具有空气和湿度不稳定、环境毒性大以及成本较高的缺点。另一方面,不含金属有机小分子发光材料因其具有分子多样性、低成本、可调能隙和可规模化生产等优点,引起了人们的广泛研究兴趣。
然而,已发展的绝大多数的有机发光体结构相对平面,其很强的分子间π-π相互作用会造成固态下荧光的淬灭,也称为ACQ现象。这种ACQ效应进一步加剧了深红/近红外固体发光分子的设计难度。
仍然需要改善的深红/近红外发光材料。
发明内容
本发明提供了新型的聚集诱导发光化合物、其制备方法及其应用。该化合物不仅克服了现有的发光材料的ACQ现象,而且在发光性质、热力学性质和/稳定性方面表现优异,从而可以用于各种应用中,例如用于发光材料(例如,荧光探针)、电子器件(特别是OLED器件)、薄膜、光刻胶、功能性涂层和/或生物成像(例如细胞内成像)等等。
具体来说,本发明提供了:
一种聚集诱导发光化合物,由下式I表示:
其中,Ar1和Ar2相同或者不同,并且各自独立地为氢、取代或未取代的成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基或其组合,在取代的情况下,芳香族环烃基和/芳香族杂环基的至少一个氢被选自卤原子、烷氧基、羟基、氨基、烯基、炔基、炔基羰基、芳基、酯基、巯基、醛基、氰基、氧原子、亚氨基、砜基、羰基、炔基酯基、亚烯基、亚炔基、亚芳基、-C(=O)OH、硫原子、亚硝基、硝基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基、成环碳原子6-18的芳香族环烃基和成环碳原子5-18的芳香族杂环基中的至少一者取代,条件是Ar1和Ar2不同时为氢;
Ar1和Ar2中的原子可以任选地与N成环;
n为0或1,
a为0或1,b为0或1,条件是a和b不同时为0;
以及
一种制备式I的化合物的方法,包括下列步骤:
在催化剂以及有机溶剂的存在下,将式III的化合物与式IV的化合物反应,从而得到式I的化合物,
其中,Ar1和Ar2相同或者不同,并且各自独立地为取代或未取代的成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基或其组合,在取代的情况下,芳香族环烃基和/芳香族杂环基的至少一个氢被选自卤原子、烷氧基、羟基、氨基、烯基、炔基、炔基羰基、芳基、酯基、巯基、醛基、氰基、氧原子、亚氨基、砜基、羰基、炔基酯基、亚烯基、亚炔基、亚芳基、-C(=O)OH、硫原子、亚硝基、硝基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基、成环碳原子6-18的芳香族环烃基和成环碳原子5-18的芳香族杂环基中的至少一者取代,条件是Ar1和Ar2不同时为氢;
Ar1和Ar2中的原子可以任选地与N成环;
n为0或1,
a为0或1,b为0或1,条件是a和b不同时为0;
A为卤素以及
任选地,所述方法还包括下列步骤:
在催化剂的存在下,将式III的化合物与式IV的化合物反应,从而得到式V的化合物,以及
在催化剂的存在下,将式V的化合物与芳香族硼酸衍生物反应,从而得到式I的化合物;
优选地,芳香族硼酸衍生物选自成环碳原子6-18的芳香族环烃基硼酸和/或成环碳原子5-18的芳香族杂环基硼酸,更优选苯硼酸、4-甲苯硼酸或4-吡啶基硼酸。
优选地,催化剂选自金属有机催化剂、有机膦催化剂、氧化催化剂或其任意组合,优选贵金属有机催化剂,更优选Pd(OAc)2、P(t-Bu)3、Pd2(dba)3、RuPhos、或其任意组合,
优选地,有机溶剂选自芳香烃类溶剂、脂肪烃溶剂、含氧杂环类溶剂,更优选甲苯、四氢呋喃。
优选地,二价芳香族基团由下式II表示:
其中,X1、X2和X3各自独立地选自C、N、O、S或其任意组合,
m为0或1,
L1表示C1-C16二价烃基、成环碳原子6-18的芳香族环烃基、成环碳原子5-18的芳香族杂环基、单键或者Ar3与苯环稠合;以及
Ar3表示取代或未取代的成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基或其组合,在取代的情况下,芳香族环烃基和/芳香族杂环基的至少一个氢被选自卤原子、烷氧基、羟基、氨基、烯基、炔基、炔基羰基、芳基、酯基、巯基、醛基、氰基、氧原子、亚氨基、砜基、羰基、炔基酯基、亚烯基、亚炔基、亚芳基、-C(=O)OH、硫原子、亚硝基、硝基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基、成环碳原子6-18的芳香族环烃基和成环碳原子5-18的芳香族杂环基中的至少一者取代。
优选地,二价芳香族基团选自下列中的至少一者:
优选地,Ar1和Ar2选自下列中的至少一者:
优选地,聚集诱导发光化合物选自下列中的至少一者:
一种有机电致发光器件,包括阴极、阳极以及阴极和阳极之间的发光层,所述发光层包含所述的聚集诱导发光化合物。
优选的,所述发光层依次包括空穴注入层、空穴传输层、发射层和电子传输层,其中所述发射层包含所述聚集诱导发光化合物。
优选地,所述有机电致发光器件的发光波长为600-1500nm,优选地,量子发射效率为1%-20%,优选地,辐射度为500-10000mW Sr-1m-2。
上述化合物用于生物成像的应用。
一种有机膜,包含所述的聚集诱导发光化合物。
附图说明
图1示出化合物BT-2ATPE的1H-NMR光谱。
图2示出化合物BT-2ATPE的13C-NMR光谱。
图3示出化合物BT-2ATPE的高分辨质谱MALDI-TOF。
图4示出化合物BT-2NATPE的1H-NMR光谱。
图5示出化合物BT-2NATPE的13C-NMR光谱。
图6示出化合物BT-2NATPE的高分辨质谱MALDI-TOF。
图7示出化合物BT-2ATPE-1Br在CD2Cl2中的1H-NMR谱。
图8示出化合物BT-2ATPE-1Br在CD2Cl2中的13C-NMR谱。
图9示出化合物BT-2ATPE-1Br的高分辨质谱MALDI-TOF。
图10示出化合物BT-NATPE-1Br在CD2Cl2中的1H-NMR谱
图11示出化合物BT-NATPE-1Br在CD2Cl2中的13C-NMR谱
图12示出化合物BT-NATPE-1Br的高分辨质谱(MALDI-TOF)
图13示出化合物BT-ATPE-Ph的1H-NMR谱图。
图14示出化合物BT-ATPE-Ph的13C-NMR谱。
图15示出化合物BT-ATPE-Ph的高分辨质谱MALDI-TOF。
图16示出化合物BT-ATPE-Py的1H-NMR谱。
图17示出化合物BT-ATPE-Py的13C-NMR谱。
图18示出化合物BT-ATPE-Py的高分辨质谱MALDI-TOF。
图19示出化合物BT-NATPE-BA的1H-NMR谱。
图20示出化合物BT-NATPE-BA的13C-NMR谱。
图21示出化合物BT-NATPE-BA的高分辨质谱(MALDI-TOF)。
图22示出:(A)BT-2ATPE和(D)BT-2NATPE在四氢呋喃(10μM)稀溶液和薄膜态的吸收和发射光谱;(B)BT-2ATPE和(E)BT-2NATPE在不同水组分(fw)THF/H2O混合物中的PL发光强度光谱。浓度:10μM;激发波长:520nm;(C,F).排放最大值和相对排放强度(I/I0)与(C)BT-2ATPE和(F)BT-2NATPE的最大发射波长以及相对荧光强度与水/THF混合物组成比例的关系。I0=纯THF中的PL强度。插图:THF稀溶液中以及粉末状态下BT-2ATPE和BT-2NATPE在365nm紫外光照射下的荧光照片。
图23示出:(A)BT-ATPE-Ph、(D)BT-ATPE-P和(G)BT-NATPE-BA在四氢呋喃(10μM)稀溶液和薄膜状态下的紫外吸收和荧光光谱;(B)BT-ATPE-Ph、(E)BT-ATPE-Py和(H)BT-NATPE-BA(B,E,H)在不同水组分(fw)THF/H2O混合物中的PL光谱。浓度:10μM每个化合物的最大吸收被选为其激发波长;(C)BT-ATPE-Ph、(F)BT-ATPE-Py、(I)BT-NATPE-BA的最大发射波长以及相对荧光强度与水/THF混合物组成比例的关系;I0=PL强度;插图:BT-ATPE-Ph、BT-ATPE-Py和BT-NATPE-BA在不同的水含量的水/THF混合物中365nm紫外光照射下的荧光照片,浓度:10μM;各化合物的最大吸收波长作为激发波长。
图24示出在不同极性溶剂中(A,B)BT-2ATPE和(D,E)BT-2NATPE的(A,D)吸收和(B,E)发射光谱;浓度:10μM;选择各溶液的最大吸收波长作为激发波长。(C,F)斯托克斯位移相对Δf的变化,Δf为溶剂极性参数。
图25示出TTB和TNB的分子结构。
图26示出:(A)TTB在不同极性溶剂中的吸收和(B)发射光谱;选择各溶液的最大吸收波长作为激发波长。(C)斯托克斯位移相对Δf的变化;Δf定义为基态与激发态间溶质偶极矩的变化。
图27示出B3LYP/6-31G(d,p)计算得到(A)BT-2ATPE和(B)BT-2NATPE气相优化几何结构。
图28示出密度泛函理论计算得到的(A)BT-2ATPE和(B)BT-2NATPE的前线轨道和能级;简称:LUMO=最低未占据分子轨道,HOMO=最高已占据分子轨道,E gap=能隙。
图29示出(A)BT-2ATPE和(B)BT-2NATPE在电解质(0.1M BuN4+PF6+二氯甲烷溶液)中的循环伏安法曲线;扫描速度为100mV/s。
图30示出氮气加热下(A)BT-2ATPE和(B)BT-2NATPE的TGA曲线,加热速度10℃/min。
图31示出氮气加热第1和第2个循环下(A)BT-2ATPE和(B)BT-2NATPE的差示扫描量热图,升温速度为10℃/min。
图32示出:(A)BT-2ATPE和BT-2NATPE的电致发光谱图。插图:设备照片;(B)BT-2ATPE和BT-2NATPE的最大辐照度;(C)电流密度-电压-亮度特性;(D)外量子效率与BT-2ATPE和BT-2NATPE EL器件中电流密度的关系。
图33示出BT-2ATPE和BT-2NATPE的CIE坐标。
图34示出不同电压下(A)BT-2ATPE和(B)BT-2NATPE的电致发光谱图。
具体实施方式
下面详细描述本发明的实施方案。下面描述的实施方案是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。实施方案中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
定义和一般术语
现在详细描述本发明的某些实施方案,其实例由随附的结构式和化学式说明。本发明意图涵盖所有的替代、修改和等同技术方案,它们均包括在如权利要求定义的本发明范围内。本领域技术人员应认识到,许多与本文所述类似或等同的方法和材料能够用于实践本发明。本发明绝不限于本文所述的方法和材料。在所结合的文献、专利和类似材料的一篇或多篇与本申请不同或相矛盾的情况下(包括但不限于所定义的术语、术语应用、所描述的技术,等等),以本申请为准。
应进一步认识到,本发明的某些特征,为清楚可见,在多个独立的实施方案中进行了描述,但也可以在单个实施例中以组合形式提供。反之,本发明的各种特征,为简洁起见,在单个实施方案中进行了描述,但也可以单独或以任意适合的子组合提供。
除非另外说明,本发明所使用的所有科技术语具有与本发明所属领域技术人员的通常理解相同的含义。本发明涉及的所有专利和公开出版物通过引用方式整体并入本发明。
除非另外说明,应当应用本文所使用的下列定义。出于本发明的目的,化学元素与元素周期表CAS版,和《化学和物理手册》,第75版,1994一致。此外,有机化学一般原理可参考“Organic Chemistry”,Thomas Sorrell,University Science Books,Sausalito:1999,和“March's Advanced Organic Chemistry”by Michael B.Smith and Jerry March,JohnWiley&Sons,New York:2007中的描述,其全部内容通过引用并入本文。
除非另有说明或者上下文中有明显的冲突,本文所使用的冠词“一”、“一个(种)”和“所述”旨在包括“至少一个”或“一个或多个”。因此,本文所使用的这些冠词是指一个或多于一个(即至少一个)宾语的冠词。例如,“一组分”指一个或多个组分,即可能有多于一个的组分被考虑在所述实施方案的实施方式中采用或使用。
术语“包含”为开放式表达,即包括本发明所指明的内容,但并不排除其他方面的内容。
另外,需要说明的是,除非以其他方式明确指出,在本发明中所采用的描述方式“各…独立地为”与“…各自独立地为”和“…独立地为”可以互换,均应做广义理解,其既可以是指在不同基团中,相同符号之间所表达的具体选项之间互相不影响,也可以表示在相同的基团中,相同符号之间所表达的具体选项之间互相不影响。
在本说明书的各部分,本发明公开化合物的取代基按照基团种类或范围公开。特别指出,本发明包括这些基团种类和范围的各个成员的每一个独立的次级组合。例如,术语“C1-18烷基”包括甲基、乙基、C3烷基、C4烷基、C5烷基和C6烷基。
在本发明的各部分,描述了连接取代基。当该结构清楚地需要连接基团时,针对该基团所列举的马库什变量应理解为连接基团。例如,如果该结构需要连接基团并且针对该变量的马库什基团定义列举了“烷基”或“芳香族基团”,则应该理解,该“烷基”或“芳基”分别代表连接的亚烷基基团或亚芳香族基团。
本发明使用的术语“烃基”包括芳香族烃基和脂肪族烃基。脂肪族烃基包括“烷基”或“烷基基团”,烯基和炔基,它们可以是饱和或不饱和的直链或支链二价烃基基团。所述烃基可以任选地被一个或多个本发明描述的取代基所取代。在本发明的一个实施方案中,烷基基团含有1-18个碳原子。在另一实施方案中,烷基基团含有1-12个碳原子;在又一实施方案中,烷基基团含有1-6个碳原子;再一实施方案中,烷基基团含有1-4个碳原子;还在一实施方案中,烷基基团含有1-3个碳原子。
烷基基团的实例包含,但并不限于,C1-12烷基,如甲基,乙基,正丙基,异丙基,正丁基,异丁基,仲丁基,叔丁基,正戊基,2-戊基,3-戊基,2-甲基-2-丁基,3-甲基-2-丁基,3-甲基-1-丁基,2-甲基-1-丁基,正己基,2-己基,3-己基,2-甲基-2-戊基,3-甲基-2-戊基,4-甲基-2-戊基,3-甲基-3-戊基,2-甲基-3-戊基,2,3-二甲基-2-丁基,3,3-二甲基-2-丁基,正庚基,正辛基,等等。
术语“二价烃基”表示从烃基中去掉两个氢原子所得到的二价基团。本发明中二价烃基包括但不限于1-16个碳原子。在一实施方案中,二价烃基含有1-6个碳原子;在另一实施方案中,二价烃基含有1-4个碳原子;在又一实施方案中,二价烃基含有1-3个碳原子;还在一实施方案中,二价烃基含有1-2个碳原子。这样的实例包括次甲基和次乙基等等。所述二价烃基任选地被一个或多个本文所描述的取代基所取代。
术语“一价烃基”表示从烃基中去掉一个氢原子所得到的一价基团。一价烃基包括但不限于1-20个碳原子。在一实施方案中,一价烃基含有1-6个碳原子;在另一实施方案中,一价烃基含有1-4个碳原子;在又一实施方案中,一价烃基含有1-3个碳原子;还在一实施方案中,一价烃基含有1-2个碳原子。这样的实例包括亚甲基、亚乙基、亚异丙基等等。所述一价烃基任选地被一个或多个本发明所描述的取代基所取代。
术语“烯基”表示碳原子的直链或支链一价烃基,其中至少有一个不饱和位点,即有一个碳-碳sp2双键,其中,所述烯基基团任选地被一个或多个本发明所描述的取代基所取代,其包括“cis”和“tans”的定位,或者"E"和"Z"的定位。在一实施方案中,烯基基团包含2-8个碳原子;在另一实施方案中,烯基基团包含2-6个碳原子;在又一实施方案中,烯基基团包含2-4个碳原子。烯基基团的实例包括,但并不限于,乙烯基、烯丙基等等。
术语“炔基”表示碳原子的直链或支链一价烃基,其中至少有一个不饱和位点,即有一个碳-碳sp三键,其中,所述炔基基团任选地被一个或多个本发明所描述的取代基所取代。在一实施方案中,炔基基团包含2-8个碳原子;在另一实施方案中,炔基基团包含2-6个碳原子;在又一实施方案中,炔基基团包含2-4个碳原子。炔基基团的实例包括,但并不限于,乙炔基、炔丙基、1-丙炔基等等。
术语“羧基”,无论是单独使用还是和其他术语连用,如“羧烷基”,表示-CO2H;术语“羰基”,无论是单独使用还是和其他术语连用,如“氨基羰基”或“酰氧基”,表示-(C=O)-。
术语“卤素”和“卤代”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。
术语“二价芳香族基团”包括从芳香环中去掉两个氢原子从而与其他基团直接连接的基团。优选地,二价芳香族基团在成环原子中具有至少一个杂原子,例如N、O或S。
术语“芳香族环烃基”包括单环、双环和三环的芳基,其中,至少一个环体系是芳香族的,其中每一个环体系包含6-18个原子组成的环。芳基基团通常,但不必须地通过芳基基团的芳香性环与母体分子连接。术语“芳基”可以和术语“芳香环”或“芳环”交换使用。芳基基团的实例可以包括苯基、联苯基、萘基和蒽。所述芳基基团任选地被一个或多个本文所描述的取代基所取代。
在本发明中,取代基可以选自卤原子、烷氧基、羟基、氨基、烯基、炔基、炔基羰基、芳基、酯基、巯基、醛基、氰基、氧原子、亚氨基、砜基、羰基、炔基酯基、亚烯基、亚炔基、亚芳基、-C(=O)OH、硫原子、亚硝基、硝基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基、成环碳原子6-18的芳香族环烃基、成环碳原子5-18的芳香族杂环基、巯基、氰基和硝基中的至少一者。
近年来,已经报道了一种聚集诱导发光(AIE)现象,这与ACQ效应正好相反。在稀溶液中,AIE发光体(AIEgen)一般表现为弱发光或无发光,而在聚集态下则表现为强发光。AIE材料的有强固态发射行为十分有利于制备非掺杂的OLED器件。
本发明中,申请人合成了多种基于芳香族环(例如2,1,3-苯并噻唑BT)的聚集诱导发光材料。这些分子在近红外/深红外(600-1500nm,优选666nm)波长范围内表现出高效的固态发射,其荧光量子产率高达(600-1500nm,优选666nm)30%-50%。在一个例子中,合成了基于BT-2ATPE的聚集诱导发光化合物,并且制备了非掺杂近红外OLED器件,其电致发光(EL)波长为684nm,高辐射度5772mW·Sr-1·m-2,EQE为1.73%。此外,申请人还合成各种对称和不对称的发光颜色可调的AIE材料,在非掺杂近红外OLED以及生物成像等方面具有很大的应用潜力。
在一个方面中,本发明提供了一种AIE化合物,其由下式I表示:
其中,Ar1和Ar2相同或者不同,并且各自独立地为氢、取代或未取代的成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基或其组合,在取代的情况下,芳香族环烃基和/芳香族杂环基的至少一个氢被选自卤原子、烷氧基、羟基、氨基、烯基、炔基、炔基羰基、芳基、酯基、巯基、醛基、氰基、氧原子、亚氨基、砜基、羰基、炔基酯基、亚烯基、亚炔基、亚芳基、-C(=O)OH、硫原子、亚硝基、硝基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基、成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基、巯基、氰基和硝基中的至少一者取代,条件是Ar1和Ar2不同时为氢;
Ar1和Ar2中的原子可以任选地与N成环;
n为0或1,
a为0或1,b为0或1,条件是a和b不同时为0;
以及
优选地,Ar1和Ar2各自独立地为下式表示的基团:Ar4-S,其中,Ar4各自独立地为成环碳原子数为5-18的芳香族烃基或芳香族杂环基团,例如苯基、萘基、苯基、萘基、蒽基、菲基、并四苯基、芘基、苯并[c]菲基、苯并菲基、芴基、苯并芴基、二苯并芴基、联苯基、三联苯基、四联苯基、荧蒽基、吡咯基、吡嗪基、吡啶基、嘧啶基、三嗪基、吲哚基、异吲哚基、咪唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、二苯并噻吩基、喹啉基、异喹啉基、喹喔啉基、咔唑基、菲啶基、吖啶基、菲咯啉基、吩嗪基、吩噻嗪基、吩噁嗪基、噁唑基、噁二唑基、呋咱基、噻吩基、苯并噻吩基、二氢吖啶基、氮杂咔唑基、喹唑啉基等,优选为吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基或氮杂咔唑基。
S为取代基,优选卤原子、烷氧基(如C1-6烷氧基)、羟基、氨基、烯基、炔基、炔基羰基、芳基(优选三苯乙烯基)、酯基、巯基、醛基、氰基、氧原子、亚氨基、砜基、羰基、炔基酯基、亚烯基、亚炔基、亚芳基、-C(=O)OH、硫原子、亚硝基和硝基中的至少一者。
更优选地,Ar1和Ar2选自下列中的至少一者:
在另一方面中,本发明还提供了一种制备式I的化合物的方法,包括下列步骤:
在催化剂以及有机溶剂的存在下,将式III的化合物与式IV的化合物反应,从而得到式I的化合物进行多组分反应,从而得到式I的聚合物,
其中,各变量如上所述,并且A为卤素,优选Br。
取决于式III的化合物与式IV的化合物的摩尔当量比,所述方法还包括下列步骤:
在催化剂的存在下,将式III的化合物与式IV的化合物反应,从而得到式V的化合物,以及
在催化剂的存在下,将式V的化合物与芳香族硼酸衍生物反应,从而得到式I的化合物;
芳香族硼酸衍生物可以选自成环碳原子6-18的芳香族环烃基硼酸和/或成环碳原子5-18的芳香族杂环基硼酸,更优选苯硼酸、4-甲苯硼酸或4-吡啶基硼酸。
催化剂可以选自金属有机催化剂、有机膦催化剂、氧化催化剂或其任意组合,优选贵金属有机催化剂,更优选Pd(OAc)2、P(t-Bu)3、Pd2(dba)3、RuPhos或其任意组合,
优选地,有机溶剂选自芳香烃类溶剂、脂肪烃溶剂、含氧杂环类溶剂,更优选甲苯、四氢呋喃。
优选地,二价芳香族杂环基团由下式II表示:
其中,X1、X2和X3各自独立地选自C、N、O、S或其任意组合,任选的条件是X1、X2和X3不同时为C,
m为0或1,
L1表示C1-C16二价烃基、成环碳原子6-18的芳香族环烃基、成环碳原子5-18的芳香族杂环基、单键或者Ar3与苯环稠合;以及
Ar3表示取代或未取代的成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基或其组合,在取代的情况下,芳香族环烃基和/芳香族杂环基的至少一个氢被选自卤原子、羟基、醛基、羧基、氨基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基、成环碳原子6-18的芳香族环烃基、取代或未取代的成环碳原子5-18的芳香族杂环基、巯基、氰基和硝基中的至少一者取代。
更优选地,二价芳香族基团为成环原子数为9-18的二价芳香族杂环基团,其中至少一个成环原子选自N、O或S中的杂原子,更优选地,选自下列中的至少一者:
所述有机溶剂可以是本领域内已知的常规溶剂,例如选自四氢呋喃、甲苯、二氯甲烷、二甲基二酰胺和氯仿中的至少一种;
优选地,合成式I的化合物的反应可以在惰性气体保护下进行,反应温度为15-120℃。
优选地,在所述方法中,反应时间为10-30小时,优选为16-20小时,更优选为16-17小时。
得到的AIE化合物表现出优异的深红/近红外固体发射特性,优异的稳定性和热力学性质,可以用于各种应用中,包括但是不限于发光材料、电子器件、薄膜、光刻胶、功能性涂层和/或生物成像。
本发明还公开一种有机电致发光器件,包括阴极、阳极以及阴极和阳极之间的发光层。所述发光层可以包含本文所述的聚集诱导发光化合物。
优选地,所述发光层依次包括空穴注入层、空穴传输层、发射层和电子传输层,其中所述发射层包含本文所述的聚集诱导发光化合物。关于形成空穴注入层、空穴传输层和电子传输层的材料,它们都是本领域内已知的。
优选地,所述有机电致发光器件的发光波长为600-150nm,优选地,量子发射效率为1%-20%,优选地,辐射度为500-10000mW Sr-1m-2。
本发明还提供了AIE化合物用于生物成像的应用。
本发明还提供了一种有机膜,包含本文所述的聚集诱导发光化合物。
例子
提供下述的例子来示意性描述以帮助本领域技术人员理解本发明。然而,本发明的以下例子不应被构建为不适当地限制本发明。在不脱离本发明发现的范围的情况下,本领域普通技术人员可以对所讨论的例子进行变化和修改。
化合物合成
在例子中,典型的化合物合成路线如下所示:
合成ATPE或NATPE
采用文献方法合成了N-苯基-4-(1,2,2-三苯乙烯基)苯胺(ATPE)和N-(4-(1,2,2-三苯基乙烯基)苯基)萘-1-胺(NATPE)。将苯胺或者1-萘胺(7.23mmol)添加至溴代四苯乙烯(1.00g,2.41mmol),Pd(OAc)2(27mg,0.12mmol),P(t-Bu)3(48mg,0.24mmol),NaOtBu(694mg,7.23mmol)和甲苯(48mL)的混合液,在氮气保护下,回流16h。混合物用二氯甲烷和水淬取,合并有机相,减压浓缩。粗品经二氯甲烷/正己烷(v/v=1:6)硅胶柱纯化,得到ATPE(产率:75%)或NATPE(产率:72%)。
合成BT-2ATPE
将ATPE(508mg,1.2mmol)、4,7-二溴苯[c]-1,2,5-噻二唑(118mg,0.4mmol)、Cs2CO3(430mg,1.2mmol)、Pd2(dba)3(37mg,0.04mmol)和RuPhos(37mg,0.08mmol)在N2下混合,加入新蒸馏甲苯(8mL)。在室温下搅拌30min,回流17h,冷却至室温,用水和二氯甲烷萃取反应混合物。收集有机层,溶剂蒸发后,以二氯甲烷/正己烷(v/v=1:4~1:1)为洗脱剂,经硅胶柱层析纯化粗品,得到BT-2ATPE为紫红色固体(310mg,79.1%)。采用二氯甲烷和甲醇重结晶进一步纯化。
1H NMR(400MHz,CD2Cl2),δ(ppm):7.23(t,4H),7.18-7.00(m,38H),6.876(dt,4H),6.753(dt,4H).13C NMR(100MHz,CD2Cl2),δ(ppm):152.6,147.6,146.1,144.2,144.0,143.8,140.9,140.8,138.5,135.8,132.3,131.6,131.6,131.5,129.3,127.9,127.8,126.6,126.6,126.5,125.0,123.9,123.2,122.6.HRMS(MALDI-TOF):m/z:[M]+C70H50N4S理论值:978.3756,实测值978.3795。
合成BT-2NATPE
将NATPE(712mg,1.5mmol)、4,7-二溴苯并[c]-1,2,5-噻二唑(174mg,0.6mmol)、Cs2CO3(600mg,1.8mmol)、Pd2(dba)3(30mg,0.03mmol)和RuPhos(30mg,0.06mmol)在N2下混合,加入蒸馏甲苯(30mL)。混合物在室温下搅拌30分钟,然后在110℃反应过夜.将混合物冷却至室温后,用水洗涤两次,用二氯甲烷萃取,以二氯甲烷/正己烷(v/v=1:4~2:1)为洗脱液,用硅胶柱色谱法纯化,得到复方BT-2NATPE为紫色固体(412mg,64.6%)。采用二氯甲烷和甲醇重结晶进一步纯化。
1H NMR(400MHz,CDCl3),δ(ppm):7.908(d,2H),7.846(d,2H),7.711(d,2H),7.466-7.426(m,2H),7.381(t,2H),7.349-7.308(m,2H),7.240(dd,2H),7.142-6.979(m,30H),6.825(s,2H),6.789(dt,4H),6.535(dt,4H).13C NMR(100MHz,CDCl3),δ(ppm):151.96,147.17,144.19,144.03,143.80,143.61,140.90,140.35,137.05,135.86,135.21,132.09,131.57,131.52,131.51,130.74,128.45,127.70,126.51,126.45,126.39,126.35,126.33,126.22,126.08,125.95,124.40,123.08,120.40.HRMS(MALDI-TOF):m/z:[M]+C78H55N4S理论值1078.4069,实测值1078.4036。
合成BT-ATPE-1Br
将ATPE(508mg,1.2mmol)、4,7-二溴苯并[c]-1,2,5-噻二唑(1056mg,3.6mmol)、Cs2CO3(1200mg,3.6mmol)、Pd2(dba)3(110mg,0.12mmol)和RuPhos(112mg,0.24mmol)在N2下混合,加入甲苯(24mL)。在室温下搅拌30min后,将反应混合物回流17h,冷却至室温,加入水,用二氯甲烷萃取。有机层结合,无水硫酸钠干燥,蒸去溶剂。以二氯甲烷/正己烷(v/v=1:4)为洗脱液,硅胶柱层析法纯化粗品,得到BT-ATPE-1Br为红色固体(660mg,73.5%)。
1H NMR(400MHz,CD2Cl2)δ(ppm):7.70(d,2H),7.26(t,2H),7.21-6.99(m,19H),6.93(d,2H),6.77(d,2H).13C NMR(100MHz,CD2Cl2)δ(ppm):155.1,151.1,147.7,146.3,144.4,144.3,144.0,141.5,141.1,140.1,139.7,133.0,132.6,131.8,131.7,129.7,128.2,127.0,126.9,124.7,124.2,123.9,123.7,107.8.HRMS(MALDI-TOF):m/z:[M]+C38H26BrN3S理论值635.1031,实测值635.1066。
合成BT-NATPE-1Br
类似于BT-ATPE-1Br的合成工艺,粗品以二氯甲烷/正己烷(v/v=1:4)为洗脱液,硅胶柱层析纯化,得到BT-NATPE-1Br为红色固体(772mg,75.0%)。
1H NMR(400MHz,CD2Cl2)δ(ppm):7.89(t,2H),7.79(d,1H),7.58(d,1H),7.48(t,1H),7.42(t,1H),7.36(t,1H),7.25-7.03(m,16H),6.88(d,2H),6.81(d,1H),6.66(d,2H).13C NMR(100MHz,CD2Cl2)δ(ppm):155.1,150.5,147.1,144.5,144.3,144.1,143.7,141.4,141.1,140.8,138.9,135.7,133.0,132.4,131.9,131.8,130.8,129.0,128.2,127.3,127.0,127.0,126.9,126.8,126.5,124.3,122.2,121.8,107.1.HRMS(MALDI-TOF):m/z:C42H28BrN3S理论值685.1187,实测值685.1153。
合成BT-NATPE-BA
在N2下,加入BT-NATPE-1Br(660mg,0.874mmol)、4-甲苯硼酸(158mg,1.049mmol)、K2CO3(482mg,3.495mmol)、Pd(PPh3)4(40.5mg,0.035mmol)、去氧水(8.7mL)和四氢呋喃(29.1mL)的混合物。反应混合物回流过夜。将反应混合物冷却至室温,水洗后用二氯甲烷萃取。有机相合并,无水Na2SO4干燥,蒸去溶剂。以二氯甲烷/正己烷(v/v=1:4)为洗脱液,硅胶柱层析法纯化粗品,得到BT-NATPE-BA为橙色固体(600mg,96.2%)。
1H NMR(400MHz,CDCl3)δ(ppm):10.08(s,1H),8.09(d,2H),8.00(d,2H),7.91(d,2H),7.80(d,1H),7.75(d,1H),7.51-7.43(m,2H),7.37-7.29(m,2H),7.19-7.02(m,15H),6.97(d,1H),6.90(d,2H),6.72(d,2H).13C NMR(100MHz,CDCl3)δ(ppm):192.1,154.7,150.6,146.8,144.2,143.9,143.7,143.7,143.5,140.9,140.9,140.8,138.6,135.5,132.3,131.7,131.6,131.5,130.7,130.1,129.7,129.5,128.6,127.9,127.8,127.1,126.7,126.6,126.5,126.4,126.2,124.1,122.2,120.4.HRMS(MALDI-TOF):m/z:[M]+C49H33N3OS理论值735.2344,实测值735.2340。
合成BT-ATPE-Ph
在N2条件下,加入BT-ATPE-Br(90mg,0.141mmol)、苯硼酸(19mg,0.156mmol)、K2CO3(78mg,0.567mmol)、Pd(PPh3)4(7mg,0.006mmol)、去氧水(1.4mL)和四氢呋喃(4.7mL)的混合物。反应混合物回流过夜。将反应混合物冷却至室温,加水,二氯甲烷萃取。有机层合并,无水硫酸钠干燥,蒸去溶剂。以二氯甲烷/正己烷(v/v=1:4~1:2)为洗脱液,硅胶柱层析法纯化粗品,得到BT-ATPE-Ph为橙色固体(89mg,99.2%)。
1H NMR(400MHz,CD2Cl2)δ(ppm):7.84(d,2H),7.53(d,1H),7.44(t,2H),7.34(t,1H),7.20-6.97(m,21H),6.85(d,2H),6.73(d,2H).13C NMR(100MHz,CD2Cl2)δ(ppm):155.5,152.1,148.0,146.6,144.5,144.4,144.2,141.4,141.2,139.4,139.3,138.2,132.6,131.9,131.8,130.1,129.7,129.1,129.0,128.4,128.2,127.0,126.9,124.5,123.9,123.5.HRMS(MALDI-TOF):m/z:[M]+C44H31N3S理论值633.2239,实测值633.2266。
合成BT-ATPE-Py
在N2下,加入BT-ATPE-1Br(90mg,0.141mmol)、4-吡啶基硼酸(20mg,0.156mmol)、K2CO3(78mg,0.567mmol)、Pd(PPh3)4(7mg,0.006mmol)、去氧水(1.4mL)和四氢呋喃(4.7mL)的混合物。反应混合物回流过夜。将反应混合物冷却至室温,用水和二氯甲烷萃取。有机相合并,无水硫酸钠干燥,蒸去溶剂。以二氯甲烷/己烷(v/v=1:4~1:2)为洗脱剂,硅胶柱层析法纯化粗品,得到BT-ATPE-Py为红色固体(80mg,87.9%)。
1H NMR(400MHz,CD2Cl2)δ(ppm):8.61(d,2H),7.82(d,2H),7.64(d,1H),7.20(t,2H),7.13-6.96(m,19H),6.86(d,2H),6.73(d,2H).13C NMR(100MHz,CD2Cl2)δ(ppm):155.0,151.7,150.5,147.8,146.3,145.2,144.5,144.3,144.1,141.6,141.1,139.9,132.6,132.5,132.4,131.9,131.8,130.0,129.8,129.1,129.0,128.2,127.0,126.9,126.0,125.0,124.4,124.0,123.7,122.9.HRMS(MALDI-TOF):m/z:[M]+C43H30N4S理论值634.2191,实测值634.2179
化合物的物理性质表征
通过紫外可见吸收和荧光光谱研究了代表性的化合物的光学性质(图22和23)。这些化合物最大吸收在480-522纳米的范围内,最大发射波长在615-674nm的范围内。不对称产物(BT-ATPE-Ph、BT-ATPE-Py和BT-NATPE-BA)的吸收波长和发射波长普遍小于对称产物(BT-2ATPE、BT-2NATPE)。如图所示,在四氢呋喃溶液中,BT-2ATPE在346/522nm处出现两个吸收峰,BT-2NATPE的吸收谱与BT-2ATPE几乎相同。与之前报道的类似物TTB和TNB相比(图25),BT-2ATPE和BT-2NATPE的分子结构更为简单,但最大吸收波长(522nm和520nm)却明显大于TTB和TNB(471nm和470nm)。BT-2ATPE和BT-2NATPE吸收波长的红移应归因于它们较强的分子内电荷转移(ICT),因为供电子氮直接连接到接受电子的BT基团上。在四氢呋喃稀溶液中,BT-2ATPE和BT-2NATPE均表现出较强的发射,发射峰分别位于666nm和658nm,远远长于TTB(616nm)和TNB(613nm)的发射。这表明,电子给体(芳胺)直接连在电子受体(BT)上是一种更有效的延长吸收和发射的途径。薄膜状态下,BT-2ATPE和BT-2NATPE的薄膜均表现出较强的荧光信号,相对于溶液,BT-2ATPE的最大发射峰为674nm,而BT-2NATPE的发射最大值没有改动(658nm)。BT-2ATPE和BT-2NATPE在溶液和薄膜状态下几乎一样的发射波长意味着BT-2ATPE和BT-2NATPE激发态的分子结构几乎不变,可能是因为良好的电子共轭以及芳基胺和BT单元之间的大位阻限制了转子自由转动或振动。分子运动受限有利于实现强的固体发射。在不同含水率的四氢呋喃/水混合物(fw)中,当向四氢呋喃溶液中加入少量水时(fw:0~40%),BT-2ATPE和BT-2NATPE的荧光强度逐渐降低,当fw超过50%时,荧光强度开始增强(图22)。BT-2ATPE和BT-2NATPE的PL的荧光特性表明它们同时具有聚集诱导发光和扭曲的分子内电荷转移特性。如图24所示,BT-2ATPE和BT-2NATPE的吸收曲线相似,随着溶剂极性的变化吸收最大值变化不大。从环己烷到四氢呋喃,随着溶剂极性的增强,BT-2ATPE和BT-2NATPE的发射分别从631nm和624nm红移至666nm和658nm,而在溶剂极性更强的二甲基亚砜中,BT-2ATPE和BT-2NATPE分别在680nm和658nm表现出一个较弱的发射。证实了BT-2ATPE和BT-2NATPE的扭曲的分子内电荷转移特征。Lippert-Mataga方程的曲线图显示,与具有扭曲的分子内电荷转移的化合物相比,BT-2ATPE和BT-2NATPE的斜率相对较小,分别为5510cm-1和5853cm-1。然而,其类似物TTB表现出更强的扭曲的分子内电荷转移,在Lippert-Mataga方程图中斜率为9807cm-1(图26)。BT-2ATPE和BT-2NATPE拥有较弱的扭曲的分子内电荷转移效应和高效的电荷转移可能源自他们的良好的分子内给受体共轭结构和不活跃的分子内运动,有助于固定分子构型.在没有苯环间隔的情况下,BT-2ATPE和BT-2NATPE的四苯乙烯分子部分靠近BT核,会产生更强的位阻,从而限制D与A单元之间的C-N键自由旋转,导致TICT效应减弱。通过积分球法测定了溶液和薄膜中BT-2ATPE和BT-2NATPE的荧光量子产率。在四氢呋喃稀溶液中,BT-2ATPE和BT-2NATPE的荧光量子产率均为32%。更重要的是,BT-2ATPE和BT-2NATPE在薄膜中的量子产率分别高达44%和30%,说明它们作为OLED器件发射层的潜力巨大。光学性质如表1所示。
表1 BT-2ATPE和BT-2NATPE的光学和热力学性质
λabs=最大吸收波长;λem=最大发射波长;HOMO=最高占据分子轨道;LUMO=最低未占据分子轨道;Td=TGA测得的5%失重温度;Tg=DSC测定的玻璃化转变温度;溶剂:氯仿
表2 BT-ATPE-Ph、BT-ATPE-Py和BT-NATPE-BA的光学性质
理论计算、电化学和热力学性质
理论计算结果表明(图27),BT-2ATPE和BT-2NATPE中BT单元与相邻芳胺的苯基有类似的扭转角为33.44-54.62度。这两种化合物的扭曲构象继承了TPE单元固有的扭曲结构以及BT单元与相邻芳胺苯环之间的大位阻。这两个分子如此庞大的构象和拥挤的结构,不仅阻止了分子间紧密的堆积,而且阻止了分子内的运动,从而产生了高的固体荧光量子产率。图28显示了两个分子的前线轨道分布。对于这两种分子来说,HOMO轨道的电子云都分布在中心的BT基团和芳香胺基团上,表明它们具有良好的分子内共轭作用。同时,LUMOs主要由BT核的轨道主导。HOMO和LUMO部分重叠,这与强PLQY的ICT效应和近红外发射一致。的DFT计算得到BT-2ATPE的HOMO和LUMO分别为-4.70eV和-2.26eV,和BT-2NATPE相当(HOMO=-4.71eV和LUMO=-2.25eV)。BT-2ATPE(2.44eV)的带隙小于BT-2NATPE(2.46eV),与实验数据一致。
除DFT计算外,通过循环伏安法(CV)测定了两种分子的HOMO和LUMO能级。如图29所示,BT-2ATPE和BT-2NATPE均表现出三个准可逆和可逆氧化波,起始氧化电压分别为0.60V和0.65V。此外,两个分子也表现出准可逆的还原波,还原势分别为1.43V和1.59V。电化学结果表明BT-2ATPE的HOMO和LUMO能级分别为5.0eV和2.97eV,而BT-2NATPE为5.1eV和2.91eV。由于HOMO能级较高,BT-2ATPE和BT-2NATPE均适合空穴运输。
发射材料的热力学性质是器件制作的重要参数,因此采用热重分析法(TGA)和差示扫描量热法(DSC)研究了发射材料的热力学性能。TGA结果表明BT-2ATPE和BT-2NATPE均表现出好的热稳定性,5%的失重温度为340℃和369℃(图30)。BT-2ATPE的DSC谱在第一次热循环中在279℃显示一个尖锐的吸热峰,对应其熔点。因为加热过程会破坏分子的有序排列,第二次热循环发现两个额外的相变峰135℃和234℃(图31)。值得注意的是,AIEgens通常具有扭曲的柔性分子构象,具有多形态性。因此,在大多数情况下,加热循环只能观察到宽相变温度和弱相变温度。而BT-2ATPE的强而尖的相变峰意味着其结构特别刚性。BT-2NATPE,只有一个玻璃化转变温度为163℃。BT-2ATPE和BT-2NATPE的相变温度较高,说明它们具有较高的形貌稳定性。
OLED器件制备和表征
OLED器件采用图案化的ITO玻璃基板,有效面积16平方毫米,表面电阻10Ωsq-1。ITO玻璃基板用洗涤剂和去离子水清洗,在烤箱120℃烘干1小时,然后用UV-臭氧处理15分钟,然后置于压力为1×10-14Pa的蒸镀仓。有机层的蒸镀速度为而后以/> 的速度蒸镀一层2nm厚的Liq层,然后以约/>的速度蒸镀Al层作为阴极。采用Keithley 2450测试仪和PR745型光谱比色仪测量了电流-电压-亮度特性和电致发光(EL)光谱。
具体的器件结构为铟锡氧化物(ITO)/2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HATCN)(5nm)/4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)(60mm)/三(4-咔唑基-9-苯基)胺(TCTA)(5nm)/BT-2ATPE或BT-2NATPE(20nm)/4,7-二苯基-1,10-菲罗啉(Bphen)(55nm)/Lip(8-羟基喹啉锂)(2nm)/Al,通过汽相沉积方法制备。其中BT-2ATPE或BT-2NATPE为发射层,HATCN为空穴注入层,TCTA为空穴传输层,Bphen为电子传输层。
研究了EL谱图如图32所示,器件性能总结如表3所示。基于BT-2ATPE和BT-2NATPE的非掺杂器件的EL发射峰分别位于684nm和682nm处,与固体膜的PL最大发射峰(674nm和658nm)相比略有红移。BT-2ATPE和BT-2NATPE的(CIE)坐标分别为(0.692,0.305)和(0.688,0.308)(图33)。这两个器件的开启电压(Von)均为4.2V。此外,EL谱图没有显示出随着驱动偏置电压的增加而发生的任何变化,表明了它们的稳定性(图34)。BT-2ATPE和BT-2NATPE器件的辐照度分别为5772mW·Sr-1·m-2和4692mW·Sr-1·m-2。此外,BT-2ATPE器件的EQE相对较高,为1.73%,高于BT-2ATPE(1.43%)。随着电流密度增加到10ma·cm-2,BT-2ATPE器件的EQE下降到1.44%,损失了最大值的16.7%,说明EQE的滚转相对较低。
表3 BT-2ATPE和BT-2NATPE的电致发光性能
可以理解的是,以上实施方案仅仅是为了说明本公开的原理而采用的示例性实施方案,然而本公开并不局限于此。对于本领域内的普通技术人员而言,在不脱离本公开的精神和实质的情况下,可以做出各种变型和改进,这些变型和改进也视为本公开的保护范围。
Claims (8)
3.根据权利要求1或2所述的聚集诱导发光化合物,其特征在于所述聚集诱导发光化合物在固态时在666nm波长下的荧光量子产率为30%-50%。
6.一种有机电致发光器件,其特征在于包括空穴注入层、空穴传输层、发射层和电子传输层,所述发射层包含权利要求1-3中任意一项所述的聚集诱导发光化合物。
7.根据权利要求6所述的有机电致发光器件,其特征在于所述有机电致发光器件的电致发光波长为684nm,辐射度为5772mW Sr-1m-2并且外量子效率为1.73%。
8.权利要求1-3中任意一项所述的聚集诱导发光化合物在制备用于生物成像的荧光探针中的应用。
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