Chowdhury Deepak, Hassan Nadira, Roy Shrestha, Sanfui Md Hussain, Nandy Preetam, Chang Mincheol, Rahaman Mostafizur, Ghosh Narendra Nath, Hasnat Mohammad A, Chattopadhyay Pijush Kanti, Maiti Dilip K, Singha Nayan Ranjan
Advanced Polymer Laboratory, Department of Polymer Science and Technology, Government College of Engineering and Leather Technology (Post Graduate), Maulana Abul Kalam Azad University of Technology, Salt Lake City, Kolkata 700106, West Bengal, India.
Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700009, West Bengal, India.
Langmuir. 2024 Oct 22;40(42):22265-22282. doi: 10.1021/acs.langmuir.4c02890. Epub 2024 Oct 9.
Herein, natural-synthetic hybrid dual-state luminescent conducting polymers (DLCPs/DLCP1-DLCP8) possessing significant optoelectrochemical properties are strategically developed by the polymerization of prop-2-enamide, cis-butenedioic acid, 2-acrylamido-2-methylpropane-1-sulfonic acid, and in situ-generated 2-(3-acrylamidopropanamido)-2-methylpropane-1-sulfonic acid alongside the grafting of gum tragacanth. The spectroscopic data of aliphatic DLCPs affirm DLCP7 as the most stable supramolecular assembly endowing optoelectronic properties. Computational calculations identified -C(═O)NH-, -C(═O)OH, -OH, and -SOH as subluminophores. The absorption spectra, excitation wavelength-/solvent-polarity-/concentration-dependent luminescence, solid state luminescence, aggregation-induced enhanced luminescence, and time-correlated single photon count (TCSPC) studies confirm the occurrence of aggregation-mediated intramolecular through-space charge transfer (ITSCT) in the excited state of DLCP7. Mulliken charge, natural bond orbital, dipole moments, and electronic potential surface analyses confirm the charge donor-acceptor system in DLCP7. Furthermore, the selective optoelectronic response of DLCP7 toward Ca/Cu(II) at 438/574 nm is explored using ultraviolet-visible spectra, TCSPC analyses, a dynamic light scattering study, and computational investigations. The chelation-enhanced luminescence and ITSCT inhibition are responsible for turn-on and turn-off detections of Ca and Cu(II), respectively. Cu(II) → Cu(I) reduction in a DLCP7 solution is inferred from electrochemical and spectroscopic analyses. The conductivities of 9.65 × 10 S cm (solid state) and 44.35 × 10 S cm (solution) in DLCP7 are validated by current-voltage and electrochemical impedance measurements. Again, strong electronic conductivities of 43.89 × 10 S cm (solid state)/53.34 × 10 S cm (solution) and 45.42 × 10 S cm (solid state)/64.81 × 10 S cm (solution) are observed in Ca-DLCP7 and Cu(II)-DLCP7, respectively.
在此，通过丙-2-烯酰胺、顺丁烯二酸、2-丙烯酰胺基-2-甲基丙烷-1-磺酸和原位生成的2-(3-丙烯酰胺基丙酰胺基)-2-甲基丙烷-1-磺酸的聚合反应，以及黄蓍胶的接枝，策略性地开发出具有显著光电化学性质的天然-合成杂化双态发光导电聚合物（DLCPs/DLCP1-DLCP8）。脂肪族DLCPs的光谱数据证实DLCP7是赋予光电性质的最稳定超分子组装体。计算计算确定-C(═O)NH-、-C(═O)OH、-OH和-SOH为亚发光团。吸收光谱、激发波长/溶剂极性/浓度依赖性发光、固态发光、聚集诱导增强发光和时间相关单光子计数（TCSPC）研究证实了在DLCP7的激发态中发生了聚集介导的分子内空间电荷转移（ITSCT）。Mulliken电荷、自然键轨道、偶极矩和电子势表面分析证实了DLCP7中的电荷供体-受体体系。此外，利用紫外可见光谱、TCSPC分析、动态光散射研究和计算研究，探索了DLCP7在438/574 nm处对Ca/Cu(II)的选择性光电响应。螯合增强发光和ITSCT抑制分别负责Ca和Cu(II)的开启和关闭检测。通过电化学和光谱分析推断出DLCP7溶液中Cu(II)→Cu(I)的还原。通过电流-电压和电化学阻抗测量验证了DLCP7中9.65×10 S cm（固态）和44.35×10 S cm（溶液）的电导率。同样，在Ca-DLCP7和Cu(II)-DLCP7中分别观察到43.89×10 S cm（固态）/53.34×10 S cm（溶液）和45.42×10 S cm（固态）/64.81×10 S cm（溶液）的强电子电导率。
