Enhancing Near-Infrared Photothermal Performance by Molecular Aggregation Optimization in Semiconductive Coordination Polymers DOI
Yan Yong, Zhenyu Li, Konggang Qu

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(47), P. 22502 - 22511

Published: Nov. 13, 2024

Near-infrared (NIR) photothermal conversion materials have recently received widespread attention due to their potential in diverse applications. However, highly efficient organic-based NIR agents remain limited. Developing strategies enhance the efficiency of and elucidating relationship between performance molecular aggregation are desired. Herein, we report two coordination polymers {[Cd2(ONDI)(ox)]·2/3(H2O)}n (1) [Ba(ONDI)(H2O)2]n (2), which ONDI2– ligands assemble into different π–π stacking arrangements. Compound 1 exhibits H-aggregation, while compound 2 displays X-aggregation. The X-aggregation extends optical absorption region enhances intensity. Consequently, demonstrates a 1.8-fold increase (68.6%) compared (38.8%), attributed more effective interactions In addition, both compounds show semiconductive properties, with conductivities 2.1 × 10–7 S/cm for 3.0 at 30 °C nitrogen atmosphere. These properties arise from synergistic effects "band-like" charge transport within crystals "hopping" across grain boundaries. By integration interesting photoelectrical responses.

Language: Английский

Reliable Diradical Characterization via Precise Singlet–Triplet Gap Calculations: Application to Thiele, Chichibabin, and Müller Analogous Diradicals DOI
Qi Sun, Jean‐Luc Brédas, Hong Li

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

Accurately calculating the diradical character (y0) of molecular systems remains a significant challenge due to scarcity experimental data and inherent multireference nature electronic structure. In this study, various quantum mechanical approaches, including broken symmetry density functional theory (BS-DFT), spin-flip time-dependent (SF-TDDFT), mixed-reference (MRSF-TDDFT), complete active space self-consistent field (CASSCF), second-order perturbation (CASPT2), multiconfigurational pair-density (MCPDFT), are employed compute singlet–triplet energy gaps (EST) y0 values in Thiele, Chichibabin, Müller analogous diradicals. By systematically comparing results from these computational methods, we identify optimally tuned long-range corrected CAM-B3LYP BS-DFT framework as most efficient method for accurately affordably predicting both EST values. Additionally, our demonstrate that (i) MRSF-TDDFT performs much better than SF-TDDFT; (ii) MCPDFT is robust determining with minimal dependence on choice space. These findings provide insight into structure investigated molecules highlight effective strategies future studies domain. Thus, work not only advances understanding but also offers practical guidelines their investigation.

Language: Английский

Citations

0
Recent Advances in Luminescence of Platinum Complexes in the Near Infrared Second Window DOI
Shingo Hattori, Kazuteru Shinozaki

ChemPhotoChem, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

The near infrared (NIR) optical window enables to observe biological tissue noninvasively through photoimaging using luminophores. Particularly, the light in NIR II region of 1000–1400 nm between strong absorption bands H 2 O and chromophores is advantageous for phototherapies deep tissue. Pt complexes possessing high emission ability luminescence tunability are expected be luminophores imaging photosensitizers photodynamic therapy. Herein, from designed by strategy extension ligand π conjugation aggregation Pt–Pt interaction recent works reviewed.

Language: Английский

Citations

0
Exceptional Second Near-Infrared Window Organic Photothermal Material for High-Temperature Applications Activated by a 1064 nm Laser DOI

Huaxin Yang,

Weifang Wang, Ping Deng

et al.

ACS Materials Letters, Journal Year: 2025, Volume and Issue: unknown, P. 1060 - 1069

Published: Feb. 17, 2025

Language: Английский

Citations

0
Interlayer Cu²⁺ Modulation of Local Electronic Structures in CuO1-x@Cu-MnO2 Core-Shell Nanoarrays for Synergistic Photothermal Formaldehyde Degradation DOI
Jianhua Liu,

Xiao Sun,

Liting Dong

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2025, Volume and Issue: unknown, P. 125279 - 125279

Published: March 1, 2025

Language: Английский

Citations

0
Photoresponsive Behavior of Triphenylamine‐Based Organic Small Molecule Emitters Involving a Photo‐Induced Charge‐Transfer Complexation Mechanism under UV Light DOI Open Access
Xiaoteng Jia, Yukun Yuan, Qi Lin

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Comprehensive Summary Stimuli‐responsive organic luminescent materials exhibit significant sensitivity to various external stimuli, among which their excellent photosensitivity is particularly prominent. This unique feature gives them great potential for applications. Herein, five small molecule emitters based on triphenylamine derivatives have been synthesized via Suzuki‐coupling reaction. These molecules fluorescence properties with quantum yields ( Φ ) all reaching over 90%. When irradiated a 365 nm UV lamp, interesting photochromic phenomena occurred in chloroform solutions. phenomenon has studied intensively by UV‐vis absorption and spectroscopy, EPR measurements, density functional theory calculations, finally, the group was used as photoinitiation precursor electron donor, photo‐induced charge transfer complex (PCTC) initiated donor successfully constructed.

Language: Английский

Citations

0
Crystalline Boron‐Centered Analogues of Müller's Hydrocarbon DOI

Guo Pan,

Qidi Bao,

Xiaona Liu

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: June 16, 2024

Comprehensive Summary Müller's hydrocarbon is a well‐known open‐shell singlet diradicaloid, yet its structural determination and redox property remain elusive due to extremely high reactivity. Herein, we report the successful synthesis full characterizations of first neutral boron‐centered analogue ( 4 ) hydrocarbon, along with dianionic 5 2− featuring three isolable states. In presence two equivalents N‐heterocyclic carbene (NHC), reduction 4,4”‐bis(triisopropylphenylbromoboryl)terphenyl 3 potassium graphite afforded NHC‐stabilized boryl diradicaloid near‐pure diradical character y 0 = 0.93). Stepwise reductions 4,4”‐bis(dimesitylboryl)terphenyl in THF yielded monoradical anion ·− dianion , respectively, accompanied by decreasing aromaticity within conjugated spacer. Experimental studies theoretical analyses revealed that both exhibit large spin distributions at boron atoms, ground states, small singlet‐triplet energy gaps.

Language: Английский

Citations

1
Frustrated Radical Pairs: From Fleeting Intermediates to Isolable Species DOI Creative Commons
Lars J. C. van der Zee, J. Hofman, Simon Mathew

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 8, 2024

Abstract We present the design and comprehensive investigation of stable para ‐substituted triarylamine–2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) radical ion pairs (RIPs) generated via single‐electron transfer (SET). quantified degree SET in both solution solid phases, utilising a suite spectroscopic techniques including IR, EPR, NMR, single‐crystal X‐ray diffraction (SC–XRD). Our findings reveal that extent is significantly influenced by nature substituents (MeO > t Bu Br) polarity solvent (MeCN DCM toluene). The pair [( p MeOPh) 3 N]⋅ + [DDQ]⋅ − was unambiguously identified using EPR UV–vis spectroscopy, its structure confirmed SC–XRD. Detailed analysis indicates an open‐shell singlet ground state with thermally accessible triplet state, as corroborated magnetic susceptibility measurements, DFT calculations. This study offers crucial insights into mechanistic pathways RIP formation tuning states, laying groundwork for future exploration their reactivity potential applications.

Language: Английский

Citations

0
Enhancing Near-Infrared Photothermal Performance by Molecular Aggregation Optimization in Semiconductive Coordination Polymers DOI
Yan Yong, Zhenyu Li, Konggang Qu

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(47), P. 22502 - 22511

Published: Nov. 13, 2024

Near-infrared (NIR) photothermal conversion materials have recently received widespread attention due to their potential in diverse applications. However, highly efficient organic-based NIR agents remain limited. Developing strategies enhance the efficiency of and elucidating relationship between performance molecular aggregation are desired. Herein, we report two coordination polymers {[Cd2(ONDI)(ox)]·2/3(H2O)}n (1) [Ba(ONDI)(H2O)2]n (2), which ONDI2– ligands assemble into different π–π stacking arrangements. Compound 1 exhibits H-aggregation, while compound 2 displays X-aggregation. The X-aggregation extends optical absorption region enhances intensity. Consequently, demonstrates a 1.8-fold increase (68.6%) compared (38.8%), attributed more effective interactions In addition, both compounds show semiconductive properties, with conductivities 2.1 × 10–7 S/cm for 3.0 at 30 °C nitrogen atmosphere. These properties arise from synergistic effects "band-like" charge transport within crystals "hopping" across grain boundaries. By integration interesting photoelectrical responses.

Language: Английский

Citations

0