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Tuning phenoxyl-substituted diketopyrrolopyrroles from quinoidal to biradical ground states through (hetero-)aromatic linkers
Chemical Science ( IF 7.6 ) Pub Date : 2020-11-11 , DOI: 10.1039/d0sc05475e Rodger Rausch 1 , Merle I S Röhr 2 , David Schmidt 1, 2 , Ivo Krummenacher 3 , Holger Braunschweig 3 , Frank Würthner 1, 2
Chemical Science ( IF 7.6 ) Pub Date : 2020-11-11 , DOI: 10.1039/d0sc05475e Rodger Rausch 1 , Merle I S Röhr 2 , David Schmidt 1, 2 , Ivo Krummenacher 3 , Holger Braunschweig 3 , Frank Würthner 1, 2
Affiliation
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Strongly fluorescent halochromic 2,6-di-tert-butyl-phenol-functionalised phenyl-, thienyl- and furyl-substituted diketopyrrolopyrrole (DPP) dyes were deprotonated and oxidised to give either phenylene-linked DPP1˙˙ biradical (y0 = 0.75) with a singlet open shell ground state and a thermally populated triplet state (ΔEST = 19 meV; 1.8 kJ mol−1; 0.43 kcal mol−1) or thienylene/furylene-linked DPP2q and DPP3q compounds with closed shell quinoidal ground states. Accordingly, we identified the aromaticity of the conjugated (hetero-)aromatic bridge to be key for modulating the electronic character of these biradicaloid compounds and achieved a spin crossover from closed shell quinones DPP2q and DPP3q to open shell biradical DPP1˙˙ as confirmed by optical and magnetic spectroscopic studies (UV/vis/NIR, NMR, EPR) as well as computational investigations (spin-flip TD-DFT calculations in combination with CASSCF(4,4) and harmonic oscillator model of aromaticity (HOMA) analysis). Spectroelectrochemical studies and comproportionation experiments further prove the reversible formation of mixed-valent radical anions for the DPP2q and DPP3q quinoidal compounds with absorption bands edging into the NIR spectral region.
中文翻译：
通过（杂）芳香族连接基将苯氧基取代的二酮吡咯并吡咯从醌基态调整为双自由基基态
将强荧光卤代变色 2,6-二叔丁基苯酚官能化苯基、噻吩基和呋喃基取代的二酮吡咯并吡咯 (DPP) 染料去质子化并氧化，得到亚苯基连接的DPP1˙˙双自由基 ( y 0 = 0.75)具有单线态开壳基态和热填充三重态（Δ E ST = 19 meV；1.8 kJ mol -1 ；0.43 kcal mol -1 ）或具有闭壳醌基态的噻吩基/亚呋喃基连接的DPP2q和DPP3q化合物。因此，我们确定了共轭（杂）芳香桥的芳香性是调节这些双自由基化合物电子特性的关键，并通过光学证实实现了从闭壳醌DPP2q和DPP3q到开壳双自由基DPP1˙˙的自旋交叉。和磁光谱研究（UV/vis/NIR、NMR、EPR）以及计算研究（自旋翻转 TD-DFT 计算结合 CASSCF(4,4) 和芳香性谐振子模型 (HOMA) 分析）。光谱电化学研究和比例化实验进一步证明了吸收带接近近红外光谱区的DPP2q和DPP3q醌型化合物可逆形成混合价自由基阴离子。
更新日期：2020-11-18
中文翻译：
通过（杂）芳香族连接基将苯氧基取代的二酮吡咯并吡咯从醌基态调整为双自由基基态
将强荧光卤代变色 2,6-二叔丁基苯酚官能化苯基、噻吩基和呋喃基取代的二酮吡咯并吡咯 (DPP) 染料去质子化并氧化，得到亚苯基连接的DPP1˙˙双自由基 ( y 0 = 0.75)具有单线态开壳基态和热填充三重态（Δ E ST = 19 meV；1.8 kJ mol -1 ；0.43 kcal mol -1 ）或具有闭壳醌基态的噻吩基/亚呋喃基连接的DPP2q和DPP3q化合物。因此，我们确定了共轭（杂）芳香桥的芳香性是调节这些双自由基化合物电子特性的关键，并通过光学证实实现了从闭壳醌DPP2q和DPP3q到开壳双自由基DPP1˙˙的自旋交叉。和磁光谱研究（UV/vis/NIR、NMR、EPR）以及计算研究（自旋翻转 TD-DFT 计算结合 CASSCF(4,4) 和芳香性谐振子模型 (HOMA) 分析）。光谱电化学研究和比例化实验进一步证明了吸收带接近近红外光谱区的DPP2q和DPP3q醌型化合物可逆形成混合价自由基阴离子。
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