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Unsymmetrically β-Functionalized π-Extended Porphyrins: Synthesis, Spectral, Electrochemical Redox Properties, and Their Utilization as Efficient Two-Photon Absorbers
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-21 , DOI: 10.1021/acs.inorgchem.2c00787 Amir Sohel Bulbul 1 , Nivedita Chaudhri 1 , Mohd Shanu 2 , Jitendra Nath Acharyya 2 , G Vijaya Prakash 2 , Muniappan Sankar 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-21 , DOI: 10.1021/acs.inorgchem.2c00787 Amir Sohel Bulbul 1 , Nivedita Chaudhri 1 , Mohd Shanu 2 , Jitendra Nath Acharyya 2 , G Vijaya Prakash 2 , Muniappan Sankar 1
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Two new series of unsymmetrically β-functionalized porphyrins, MTPP(NO2)MA (1M), (MA = methyl acrylate) and MTPP(NO2)MB (2M) (MB = mono-benzo) (where M = 2H, Co(II), Ni(II), Cu(II) and Zn(II)), were synthesized and characterized by various spectroscopic techniques. The saddle shape conformation of ZnTPP(NO2)MAPy and ZnTPP(NO2)MB was confirmed by single-crystal X-ray analysis. Density functional theory (DFT) calculation revealed that NiTPP(NO2)MB has a severe nonplanar geometry possessing a high magnitude of ΔCβ = ±0.727 Å and Δ24 = ±0.422 Å values among all other porphyrins. Synthesized β-substituted porphyrins exhibited red-shifted B- and Q-bands corresponding to their parent molecule due to the electron-withdrawing peripheral substituents. Notable redshift (Δλmax = 50–60 nm) in electronic spectral features and with weak-intensity emission spectral features were observed for the free-base porphyrins and Zn(II) complexes compared to H2TPP and ZnTPP, respectively. The first-ring reduction potential of MTPP(NO2)MA (1M) exhibited 0.21–0.5 V anodic shift, whereas 0.18–0.23 V anodic shift was observed in the first-ring oxidation potential compared to the corresponding MTPPs due to the presence of electron-withdrawing β-substituents at the periphery of the macrocycle. Interestingly, NiTPP(NO2)MA (1Ni) has shown an additional NiII/NiIII oxidation potential observed at 2.05 V along with two ring-centered oxidations. The first-ring reduction and oxidation potentials of MTPP(NO2)MB (2M) have shown 0.39–0.46 and 0.19–0.27 V anodic shifts with respect to their corresponding MTPPs. The nonlinear optical (NLO) properties of all of the porphyrins were investigated, and the extracted nonlinear optical parameters revealed intense reverse-saturable absorption (RSA) behavior and the self-focusing behavior with positive nonlinear refractive index in the range of (0.19–1.75) × 10–17 m2/W. Zn(II) complexes exhibited the highest two-photon absorption coefficient (β) and cross section (σTPA) of ∼95 × 10–12 m/W and 19.66 × 104 GM, respectively, among all of the metal complexes.
中文翻译：
不对称 β-功能化 π-扩展卟啉：合成、光谱、电化学氧化还原性质及其作为高效双光子吸收剂的应用
两个新系列的不对称β-官能化卟啉，MTPP(NO 2 )MA ( 1M ), (MA = 丙烯酸甲酯) 和 MTPP(NO 2 )MB ( 2M ) (MB = 单苯并) (其中 M = 2H, Co (II)、Ni(II)、Cu(II) 和 Zn(II))，通过各种光谱技术合成和表征。单晶X射线分析证实了ZnTPP(NO 2 )MAPy和ZnTPP(NO 2 )MB的鞍形构象。密度泛函理论 (DFT) 计算表明，NiTPP(NO 2 )MB 具有严重的非平面几何形状，在所有其他卟啉中具有很高的 ΔC β = ±0.727 Å 和 Δ24 = ±0.422 Å 值。合成β由于吸电子外围取代基，-取代的卟啉表现出与其母体分子相对应的红移B-和Q-带。与 H 2 TPP 和 ZnTPP相比，游离碱卟啉和 Zn(II) 配合物的电子光谱特征显着红移（Δλ max = 50–60 nm），发射光谱特征较弱。由于存在_ _ _大环外围的吸电子β-取代基。有趣的是，NiTPP(NO2 )MA ( 1Ni ) 在 2.05 V 时显示出额外的 Ni II /Ni III氧化电位以及两个环中心氧化。MTPP(NO 2 )MB ( 2M )的第一环还原和氧化电位相对于其相应的 MTPP 分别显示了 0.39–0.46 和 0.19–0.27 V 阳极位移。研究了所有卟啉的非线性光学（NLO）特性，提取的非线性光学参数揭示了强烈的反向饱和吸收（RSA）行为和自聚焦行为，正非线性折射率在（0.19-1.75）范围内) × 10 –17 m 2/W。在所有金属配合物中， Zn(II) 配合物的双光子吸收系数 ( β ) 和截面 ( σTPA ) 最高，分别为 ~95 × 10 –12 m/W 和 19.66 × 10 4 GM。
更新日期：2022-06-21
中文翻译：
不对称 β-功能化 π-扩展卟啉：合成、光谱、电化学氧化还原性质及其作为高效双光子吸收剂的应用
两个新系列的不对称β-官能化卟啉，MTPP(NO 2 )MA ( 1M ), (MA = 丙烯酸甲酯) 和 MTPP(NO 2 )MB ( 2M ) (MB = 单苯并) (其中 M = 2H, Co (II)、Ni(II)、Cu(II) 和 Zn(II))，通过各种光谱技术合成和表征。单晶X射线分析证实了ZnTPP(NO 2 )MAPy和ZnTPP(NO 2 )MB的鞍形构象。密度泛函理论 (DFT) 计算表明，NiTPP(NO 2 )MB 具有严重的非平面几何形状，在所有其他卟啉中具有很高的 ΔC β = ±0.727 Å 和 Δ24 = ±0.422 Å 值。合成β由于吸电子外围取代基，-取代的卟啉表现出与其母体分子相对应的红移B-和Q-带。与 H 2 TPP 和 ZnTPP相比，游离碱卟啉和 Zn(II) 配合物的电子光谱特征显着红移（Δλ max = 50–60 nm），发射光谱特征较弱。由于存在_ _ _大环外围的吸电子β-取代基。有趣的是，NiTPP(NO2 )MA ( 1Ni ) 在 2.05 V 时显示出额外的 Ni II /Ni III氧化电位以及两个环中心氧化。MTPP(NO 2 )MB ( 2M )的第一环还原和氧化电位相对于其相应的 MTPP 分别显示了 0.39–0.46 和 0.19–0.27 V 阳极位移。研究了所有卟啉的非线性光学（NLO）特性，提取的非线性光学参数揭示了强烈的反向饱和吸收（RSA）行为和自聚焦行为，正非线性折射率在（0.19-1.75）范围内) × 10 –17 m 2/W。在所有金属配合物中， Zn(II) 配合物的双光子吸收系数 ( β ) 和截面 ( σTPA ) 最高，分别为 ~95 × 10 –12 m/W 和 19.66 × 10 4 GM。
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