Dhindsa Jasveer S, Melenbacher Adyn, Barbon Stephanie M, Stillman Martin J, Gilroy Joe B
Department of Chemistry, The University of Western Ontario, London, ON, CanadaN6A 5B7.
Dalton Trans. 2020 Nov 25;49(45):16133-16142. doi: 10.1039/c9dt03417j.
The combination of π-conjugated organic compounds and Pt(ii)-acetylides is a powerful strategy for the production of functional optoelectronic materials. The presence of the heavy element, Pt, in these compounds enhances electronic delocalization generally resulting in low-energy absorption and emission maxima and often leads to intersystem crossing, resulting in phosphorescence. When boron complexes of N-donor ligands, such as boron dipyrromethenes (BODIPYs), are involved the molecular and polymeric materials produced have properties that are advantageous for their use as oxygen-sensors, in triplet-triplet annihilation, and as the functional components of photovoltaics. Based on these exciting results, we endeavored to thoroughly examine the effect of Pt(ii)-acetylide conjugation on the properties of BF2 formazanate dyes, which offer improved redox properties and red-shifted absorption and emission bands compared to many structurally related BODIPYs. The results showed that phosphine-supported Pt(ii)-acetylide incorporation enhanced electronic conjugation, rendering the electrochemical reduction of the BF2 formazanate dyes more difficult, while also red-shifting their absorption and emission maxima. Unlike similar BODIPYs, the presence of Pt(ii) did not facilitate phosphorescence, but rather quenched fluorescence. This study provides significant insights into structure-property relationships and guiding principles for the design of BF2 formazanate dyes, a rapidly emerging family of readily accessible optoelectronic materials.
π共轭有机化合物与Pt（II）-乙炔化物的结合是制备功能性光电材料的有效策略。这些化合物中重金属元素Pt的存在增强了电子离域，通常导致低能量吸收和发射最大值，并且常常导致系间窜越，从而产生磷光。当涉及含氮供体配体的硼配合物，如硼二吡咯亚甲基（BODIPY）时，所制备的分子材料和聚合物材料具有有利于用作氧传感器、用于三重态-三重态湮灭以及用作光伏功能组件的性质。基于这些令人兴奋的结果，我们努力深入研究Pt（II）-乙炔化物共轭对BF2甲脒染料性质的影响，与许多结构相关的BODIPY相比，BF2甲脒染料具有更好的氧化还原性质以及红移的吸收和发射带。结果表明，膦负载的Pt（II）-乙炔化物的引入增强了电子共轭，使BF2甲脒染料的电化学还原更加困难，同时也使其吸收和发射最大值发生红移。与类似的BODIPY不同，Pt（II）的存在并没有促进磷光，而是淬灭了荧光。这项研究为BF2甲脒染料（一类迅速兴起的易于获得的光电材料）的结构-性质关系和设计指导原则提供了重要见解。
