syn-Diarylphthalimidoporphyrins: Effects of Symmetry Breaking on Two-Photon Absorption and Linear Photophysical Properties.
syn-Diarylphthalimidoporphyrins: Effects of Symmetry Breaking on Two-Photon Absorption and Linear Photophysical Properties.
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DOI：
10.1021/acs.jpca.1c01652
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发表时间：
2021-04-15
期刊：
影响因子：
--
通讯作者：
Vinogradov SA
中科院分区：
文献类型：
--
作者：
Allu SR;Ravotto L;Troxler T;Vinogradov SA
芳香族π扩展的卟啉化合物具有非常强的单光子(1P)和有时双光子(2P)吸收带，对构建光学成像探针和光动力学试剂具有重要意义。在这里，我们研究了破坏分子对称性对π扩展的卟啉的线性和2PA性质的影响。首先，我们开发了与两个邻苯二甲酰亚胺片段融合的卟啉的合成，称为缩二芳基邻苯二甲酰亚胺卟啉(DAPIP)。其次，测量了氢、锌、钯和铂DAPIP的光物理性质，并与完全对称的四芳基邻苯二甲酰亚胺卟啉(TAPIP)的光物理性质进行了比较。使用DFT/TDDFT计算和状态和(SOS)形式对数据进行了解释。总体而言，DAPIP中的2PA图像与中心对称的卟啉相似，这表明对称性破坏，即使是合成邻苯二甲酰亚胺融合，也会对卟啉的电子结构造成相对较小的扰动。总体而言，DAPIP的紧凑尺寸、多功能合成、高1pA和2pA横截面以及明亮的发光使DAPIP成为构建成像探针和其他生物应用的宝贵发色团。
Aromatically π-extended porphyrins possess exceptionally intense one-photon (1P) and sometimes two-photon (2P) absorption bands, presenting interest for construction of optical imaging probes and photodynamic agents. Here we investigated how breaking the molecular symmetry affects linear and 2PA properties of π-extended porphyrins. First, we developed the synthesis of porphyrins fused with two phthalimide fragments, termed syn-diarylphthalimidoporphyrins (DAPIP). Secondly, the photophysical properties of H2, Zn, Pd and Pt DAPIP were measured and compared to those of fully-symmetric tetraarylphthalimidoporphyrins (TAPIP). The data were interpreted using DFT/TDDFT calculations and Sum-Over-States (SOS) formalism. Overall, the picture of 2PA in DAPIP was found to resemble that in centrosymmetric porphyrins, indicating that symmetry breaking, even as significant as by syn-phthalimido-fusion, induces a relatively small perturbation to the porphyrin electronic structure. Collectively, the compact size, versatile synthesis, high 1PA and 2PA cross-sections and bright luminescence makes DAPIP valuable chromophores for construction of imaging probes and other bio-applications.
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影响因子：
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