Carbene derived diradicaloids - building blocks for singlet fission?

被引:65
|
作者
Messelberger, Julian [1 ]
Gruenwald, Annette [1 ]
Pinter, Piermaria [2 ]
Hansmann, Max M. [3 ]
Munz, Dominik [1 ]
机构
[1] Friedrich Alexander Univ Erlangen Nurnberg, Anorgan & Allgemeine Chem, Egerlandstr 1, D-91058 Erlangen, Germany
[2] Tech Univ Dresden, Phys Organ Chem, Bergstr 66, D-01069 Dresden, Germany
[3] Georg August Univ Gottingen, Inst Organ & Biomol Chem, Tammannstr 2, D-37073 Gottingen, Germany
关键词
DENSITY-FUNCTIONAL THEORY; N-HETEROCYCLIC CARBENES; SHELL SINGLET; BROKEN-SYMMETRY; BIS(TRIARYLAMINE) DICATIONS; MOLECULAR DESIGN; GROUND-STATE; AB-INITIO; THEORETICAL PREDICTION; ELECTRONIC-STRUCTURE;
D O I
10.1039/c8sc01999a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Organic singlet diradicaloids promise application in non-linear optics, electronic devices and singlet fission. The stabilization of carbon allotropes/cumulenes (C-1, C-2, C-4) by carbenes has been equally an area of high activity. Combining these fields, we showed recently that carbene scaffolds allow as well for the design of diradicaloids. Herein, we report a comprehensive computational investigation (CASSCF/NEVPT2; fractional occupation DFT) on the electronic properties of carbene-bridge-carbene type diradicaloids. We delineate how to adjust the properties of these ensembles through the choice of carbene and bridge and show that already a short C-2 bridge results in remarkable diradicaloid character. The choice of the carbene separately tunes the energies of the S-1 and T-1 excited states, whereas the bridge adjusts the overall energy level of the excited states. Accordingly, we develop guidelines on how to tailor the electronic properties of these molecules. Of particular note, fractional occupation DFT is an excellent tool to predict singlet-triplet gaps.
引用
收藏
页码:6107 / 6117
页数:11
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