Coordination Nanosheets Based on Terpyridine-Zinc(II) Complexes: As Photoactive Host Materials
Coordination Nanosheets Based on Terpyridine-Zinc(II) Complexes: As Photoactive Host Materials
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DOI：
10.1021/jacs.6b12810
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发表时间：
2017-04-19
影响因子：
15
通讯作者：
Nishihara, Hiroshi
中科院分区：
文献类型：
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作者：
Tsukamoto, Takamasa;Takada, Kenji;Nishihara, Hiroshi
由三向联吡啶(Tpy)配体和锌(II)离子组成的光致发光配位纳米片(CONASH)是通过允许这两个组分在液/液界面上相互反应而形成的。利用自下而上的CONASH，或有机配体设计和配位方式的灵活性，我们展示了TPY-锌(II)CONASH在结构和光功能上的多样性。1，3，6-tris[4-(4‘-2，2’：6‘，2“-terpyridyl)phenyl]benzene(1)和Zn(BF4)(2)的结合形成了具有双(Tpy)锌络合物(1-Zn)基序的阳离子CONASH，而用ZnSO4取代锌源实现了具有[Zn-2(Mu-O2SO2)(2)(Tpy)(2)]基序[1-Zn-2(SO4)(2)]的电荷中性CONASH。这种差异源于非配位(BF4-)或配位和桥联(SO42-)阴离子的使用。配位方式的改变改变了发光(1-锌中480 nm为蓝色，1-锌-2(SO4)(2)中为552 nm黄色)。光物理性质也不同，1-锌-2(SO4)(2)表现出溶剂发光变色，而1-锌没有。光致发光也受到TPY配体结构的调制。2-锌含有三芳胺中心的联吡啶配体2，并具有双(Tpy)锌基序；与1-锌相比，它的发射基本上红移(590 nm橙色)。CONASH的1-锌和2-锌具有带反阴离子(BF，-)的阳离子纳米片状骨架，因此具有阴离子交换能力。事实上，这些纳米片吸收了阴离子黄原烯染料，它们经历了来自宿主CONASH的准定量激子迁移。这一系列的研究表明，TPY-锌(II)CONASH是一种很有前途的光功能纳米材料。
Photoluminescent coordination nanosheets (CONASHs) comprising threeway terpyridine (tpy) ligands and zinc(II) ions are created by allowing the two constitutive components to react with each other at a liquid/liquid interface. Taking advantage of bottom-up CONASHs, or flexibility in organic ligand design and coordination modes, we demonstrate the diversity of the tpy-zinc(II) CONASH in structures and photofunctions. A combination of 1,3,6-tris[4-(4'-2,2':6',2"-terpyridyl)phenyl]benzene (1) and Zn(BF4)(2) affords a cationic CONASH featuring the bis(tpy)Zn complex motif (1-Zn), while substitution of the zinc source with ZnSO4 realizes a charge-neutral CONASH with the [Zn-2(mu-O2SO2)(2)(tpy)(2)] motif [1-Zn-2(SO4)(2)]. The difference stems from the use of noncoordinating (BF4-) or coordinating and bridging (SO42-) anions. The change in the coordination mode alters the luminescence (480 nm blue in 1-Zn; 552 nm yellow in 1-Zn-2(SO4)(2)). The photophysical property also differs in that 1-Zn-2(SO4)(2) shows solvatoluminochromism, whereas 1-Zn does not. Photoluminescence is also modulated by the tpy ligand structure. 2-Zn contains triarylamine-centered terpyridine ligand 2 and features the bis(tpy)Zn motif; its emission is substantially red-shifted (590 nm orange) compared with that of 1-Zn. CONASHs 1-Zn and 2-Zn possess cationic nanosheet frameworks with counteranions (BF,-), and thereby feature anion exchange capacities. Indeed, anionic xanthene dyes were taken up by these nanosheets, which undergo quasi-quantitative exciton migration from the host CONASH. This series of studies shows tpy-zinc(II) CONASHs as promising potential photofunctional nanomaterials.