“金屬配合物激發(fā)態(tài)的基礎(chǔ)與應(yīng)用研究”年度報(bào)告

支志明 程剛 陳勇

摘要：應(yīng)用量子理論，在Marcus理論基礎(chǔ)之上，研究了藍(lán)色磷光體系三芳基Pt配合物的發(fā)光性質(zhì)，并提出了量子效率優(yōu)化方案。扭曲結(jié)構(gòu)D-A分子具有局域和電荷轉(zhuǎn)移雜化態(tài)HLCT性質(zhì)，在理論上形成單三線態(tài)激子時(shí)也有可能突破量子自旋統(tǒng)計(jì)，即單線態(tài)激子的形成比例會(huì)超過(guò)25%，同時(shí)材料本身也有著較高的光致發(fā)光效率，因而在電致發(fā)光器件方面可能會(huì)有很好的性能。設(shè)計(jì)合成了一系列含有配位碳原子的四齒配體，并進(jìn)一步合成了基于這些剛性配體的鉑（II）配合物，通過(guò)穩(wěn)態(tài)光譜和超快光譜對(duì)鉑（II）配合物的光物理性質(zhì)進(jìn)行了深入研究，利用密度泛函理論對(duì)配合物的基態(tài)和激發(fā)態(tài)性質(zhì)進(jìn)行了理論分析，總結(jié)了電荷躍遷位置和類型變化的控制因素，探索了這些強(qiáng)磷光材料在光電器件中的應(yīng)用。在強(qiáng)磷光發(fā)射和長(zhǎng)激發(fā)態(tài)壽命的金（III）和鈀（II）配合物及其在光催化太陽(yáng)能轉(zhuǎn)換、能量上轉(zhuǎn)換、雙光子吸收和磷光OLED中的應(yīng)用等方面取得了階段性進(jìn)展。在廉價(jià)金屬（鋅、銅和鎢）配合物熒光/磷光材料的設(shè)計(jì)合成及光電應(yīng)用、不含金屬的有機(jī)小分子磷光發(fā)射方面取得突破性進(jìn)展，觀察到了有機(jī)分子的電致磷光。以三核吡唑基d10金屬（CuI，AgI，AuI）配位單元為主要研究對(duì)象，通過(guò)合成和配體設(shè)計(jì)對(duì)三核單元間的聚集態(tài)結(jié)構(gòu)進(jìn)行調(diào)節(jié)，實(shí)現(xiàn)了對(duì)其聚集體的光物理過(guò)程的調(diào)控。（6）利用晶態(tài)光功能配位超分子聚集體的協(xié)同作用、異相反應(yīng)和動(dòng)態(tài)孔性，進(jìn)行了研磨致發(fā)光變色、異相催化和染料降解、選擇性發(fā)光傳感等應(yīng)用研究。對(duì)于非晶相光功能配位超分子聚集體這類軟物質(zhì)材料，主要探索了其在納米結(jié)構(gòu)和生物體系中的抗癌活性等方面的應(yīng)用研究。將動(dòng)態(tài)共價(jià)鍵引入到超分子聚集體的合成中，通過(guò)次級(jí)組分自組裝的技術(shù)，成功制備了兩類新型的咪唑配位超分子聚集體，首次實(shí)現(xiàn)了次級(jí)組分自組裝合成，為合成新的光功能配位超分子聚集體提供了新思路。（8）設(shè)計(jì)和合成了16個(gè)光敏劑和催化劑。系統(tǒng)研究了這些化合物光的吸收、電子的激發(fā)和電荷傳遞過(guò)程。在電子給體存在時(shí)，對(duì)三組分光催化制氫體系的產(chǎn)氫活性進(jìn)行了研究。此外，對(duì)光催化化學(xué)轉(zhuǎn)換研究和轉(zhuǎn)換機(jī)制研究也取得了新的研究結(jié)果。發(fā)現(xiàn)了具有低三線態(tài)能級(jí)的藍(lán)光磷光主體材料，為新型磷光主體材料的設(shè)計(jì)提供了新的思路；提出了“Hot exciton”機(jī)理及雜化局域-電荷轉(zhuǎn)移（HLCT）態(tài)材料，有可能成為低成本高效率的新一代材料。

關(guān)鍵詞：金屬配合物；理論計(jì)算；高效率；長(zhǎng)激發(fā)態(tài)壽命；有機(jī)發(fā)光器件；配位超分子聚集體；磷光；光催化

Annual report of "excited states of metal complexes： basic research and applications"

Abstract：（i）Combining Marcus theory with tight binding DFT， a new high efficient luminescent material was designed based on the detailed exploration of excited state and radiation constant of a serials of Pt complex. A twisting donor–acceptor TPA-NZP exhibits fluorescent emission through a hybridized local and HLCT. （ii） Designed and synthesized a series of rigid Pt（II） complexes with tetradentate ligands. Through a combination of ultra-fast spectroscopic characterizations and theoretical calculations， we investigated detailedly the photophysical properties of these metal complexes， summarized the basic rules for tuning of the excited-state properties of metal complexes， and explored their applications in optoelectronic materials. （iii） Made progress in the application of strongly luminescent Au（III） and Pd（II） complexes with long-lived excited states on photophysics， photochemistry， and OLEDs. （iv） designed and synthesized inexpensive metal complexes （Zn， Cu， W complexes） and organic molecules for photocatalysis and OLEDs. （v） Taking trinuclear d10 metal pyrazolates as structural units， the regulation of photophysical process of these aggregates were realized by adjusting the structure of these trinuclear aggregates. （vi） Utilizing the inherent properties of synergistic interactions， heterogeneous reactions， dynamic porosity in crystalline aggregates， the application of mechanochromism， heterogeneous catalysis， dye degradation and selective luminescence sensor were achieved. （vii） Introducing dynamic covalent bond into the synthesis of coordination supramolecular aggregates， two kinds of imidazolate coordination supramolecular aggregates were prepared through subcomponent self-assembly. （viii） Designed and prepared 16 metal complexes as photosensitizers and catalysts， systematically investigated their UV absorption， electron excitation and transfer processes. Investigated the photocatalytic hydrogen production activities of theses complexes in the presence of a sacrificial electron donor in a three component photocatalytic system. （ix） Designed and synthesized low-triplet-energy host materials for blue phosphor， and provided a new idea for the design of host materials. Proposed the concept of "hot exciton " and HLCT matrials， which present a kind of new low-cost and high-efficiency fluorescence materials. Developed a type of interface technology by sol-gel methods that significantly improved the lifetime of the device.

Keywords：Metal complexes； theoretical calculation； high efficiency； long-lived excited states； organic light-emitting devices； coordination supramolecular aggregates； phosphorescence； photocatalysis

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