@article{rosko_wheeler_alameh_faulkner_durand_castellano_2024, title={Enhanced Visible Light Absorption in Heteroleptic Cuprous Phenanthrolines}, volume={63}, ISSN={["1520-510X"]}, url={https://doi.org/10.1021/acs.inorgchem.3c04024}, DOI={10.1021/acs.inorgchem.3c04024}, abstractNote={This work presents a series of Cu(I) heteroleptic 1,10-phenanthroline chromophores featuring enhanced UVA and visible-light-harvesting properties manifested through vectorial control of the copper-to-phenanthroline charge-transfer transitions. The molecules were prepared using the HETPHEN strategy, wherein a sterically congested 2,9-dimesityl-1,10-phenanthrolne (mesPhen) ligand was paired with a second phenanthroline ligand incorporating extended π-systems in their 4,7-positions. The combination of electrochemistry, static and time-resolved electronic spectroscopy, 77 K photoluminescence spectra, and time-dependent density functional theory calculations corroborated all of the experimental findings. The model chromophore, [Cu(mesPhen)(phen)]+ (1), lacking 4,7-substitutions preferentially reduces the mesPhen ligand in the lowest energy metal-to-ligand charge-transfer (MLCT) excited state. The remaining cuprous phenanthrolines (2-4) preferentially reduce their π-conjugated ligands in the low-lying MLCT excited state. The absorption cross sections of 2-4 were enhanced (εMLCTmax = 7430-9980 M-1 cm-1) and significantly broadened across the UVA and visible regions of the spectrum compared to 1 (εMLCTmax = 6494 M-1 cm-1). The excited-state decay mechanism mirrored those of long-lived homoleptic Cu(I) phenanthrolines, yielding three distinguishable time constants in ultrafast transient absorption experiments. These represent pseudo-Jahn-Teller distortion (τ1), singlet-triplet intersystem crossing (τ2), and the relaxed MLCT excited-state lifetime (τ3). Effective light-harvesting from Cu(I)-based chromophores can now be rationalized within the HETPHEN strategy while achieving directionality in their respective MLCT transitions, valuable for integration into more complex donor-acceptor architectures and longer-lived photosensitizers.}, number={3}, journal={INORGANIC CHEMISTRY}, author={Rosko, Michael C. and Wheeler, Jonathan P. and Alameh, Reem and Faulkner, Adrienne P. and Durand, Nicolas and Castellano, Felix N.}, year={2024}, month={Jan}, pages={1692–1701} }
 @article{mhanna_durand_savel_akdas-kilig_abdallah_versace_soppera_fillaut_sojic_malval_2022, title={Micropatterning of Electrochemiluminescent Polymers based on Multipolar Ru-Complexes Two-Photon Initiators.}, url={http://dx.doi.org/10.1039/d2cc04159f}, DOI={10.1039/d2cc04159f}, abstractNote={A highly two-photon active multipolar Ru-complex is used as a reactive photoinitiator for the direct integration and microstructuration of ECL-active materials on electroactive substrates.}, journal={Chemical Communications}, publisher={Royal Society of Chemistry (RSC)}, author={Mhanna, Rana and Durand, Nicolas and Savel, Paul and Akdas-Kilig, Huriye and Abdallah, Stephania and Versace, Davy-Louis and Soppera, Olivier and Fillaut, Jean-Luc and Sojic, Neso and Malval, Jean-Pierre}, year={2022}, month={Aug} }
 @article{huffman_bein_atallah_donley_alameh_wheeler_durand_harvey_kessinger_chen_et al._2022, title={Surface Immobilization of a Re(I) Tricarbonyl Phenanthroline Complex to Si(111) through Sonochemical Hydrosilylation}, volume={12}, ISSN={["1944-8252"]}, url={https://doi.org/10.1021/acsami.2c17078}, DOI={10.1021/acsami.2c17078}, abstractNote={A sonochemical-based hydrosilylation method was employed to covalently attach a rhenium tricarbonyl phenanthroline complex to silicon(111). fac-Re(5-(p-Styrene)-phen)(CO)3Cl (5-(p-styrene)-phen = 5-(4-vinylphenyl)-1,10-phenanthroline) was reacted with hydrogen-terminated silicon(111) in an ultrasonic bath to generate a hybrid photoelectrode. Subsequent reaction with 1-hexene enabled functionalization of remaining atop Si sites. Attenuated total reflectance-Fourier transform infrared spectroscopy confirms attachment of the organometallic complex to silicon without degradation of the organometallic core, supporting hydrosilylation as a strategy for installing coordination complexes that retain their molecular integrity. Detection of Re(I) and nitrogen by X-ray photoelectron spectroscopy (XPS) further support immobilization of fac-Re(5-(p-styrene)-phen)(CO)3Cl. Cyclic voltammetry and electrochemical impedance spectroscopy under white light illumination indicate that fac-Re(5-(p-styrene)-phen)(CO)3Cl undergoes two electron reductions. Mott-Schottky analysis indicates that the flat band potential is 239 mV more positive for p-Si(111) co-functionalized with both fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene than when functionalized with 1-hexene alone. XPS, ultraviolet photoelectron spectroscopy, and Mott-Schottky analysis show that functionalization with fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene introduces a negative interfacial dipole, facilitating reductive photoelectrochemistry.}, journal={ACS APPLIED MATERIALS & INTERFACES}, author={Huffman, Brittany L. and Bein, Gabriella P. and Atallah, Hala and Donley, Carrie L. and Alameh, Reem T. and Wheeler, Jonathan P. and Durand, Nicolas and Harvey, Alexis K. and Kessinger, Matthew C. and Chen, Cindy Y. and et al.}, year={2022}, month={Dec} }
 @article{durand_amar_mhanna_akdas-kiliç_soppera_malval_boucekkine_fillaut_2022, title={Two-Photon Absorption Cooperative Effects within Multi-Dipolar Ruthenium Complexes: The Decisive Influence of Charge Transfers}, volume={27}, url={http://dx.doi.org/10.3390/molecules27051493}, DOI={10.3390/molecules27051493}, abstractNote={One- and two-photon characterizations of a series of hetero- and homoleptic [RuL3-n(bpy)n]2+ (n = 0, 1, 2) complexes carrying bipyridine π-extended ligands (L), have been carried out. These π-extended D−π−A−A−π−D-type ligands (L), where the electron donor units (D) are based on diphenylamine, carbazolyl, or fluorenyl units, have been designed to modulate the conjugation extension and the donating effect. Density functional theory calculations were performed in order to rationalize the observed spectra. Calculations show that the electronic structure of the π-extended ligands has a pronounced effect on the composition of HOMO and LUMO and on the metallic contribution to frontier MOs, resulting in strikingly different nonlinear properties. This work demonstrates that ILCT transitions are the keystone of one- and two-photon absorption bands in the studied systems and reveals how much MLCT and LLCT charge transfers play a decisive role on the two-photon properties of both hetero- and homoleptic ruthenium complexes through cooperative or suppressive effects.}, number={5}, journal={Molecules}, publisher={MDPI AG}, author={Durand, Nicolas and Amar, Anissa and Mhanna, Rana and Akdas-Kiliç, Huriye and Soppera, Olivier and Malval, Jean-Pierre and Boucekkine, Abdou and Fillaut, Jean-Luc}, year={2022}, month={Feb}, pages={1493} }
 @article{durand_mhanna_savel_akdas-kiliç_malval_soppera_fillaut_2020, title={Unexpected disruption of the dimensionality-driven two-photon absorption enhancement within a multipolar polypyridyl ruthenium complex series}, volume={56}, url={http://dx.doi.org/10.1039/d0cc05025c}, DOI={10.1039/d0cc05025c}, abstractNote={The dimensionality-induced two-photon absorption enhancement is rationalized within a multipolar Ru-complex series with an unexpected disruptive effect emerging from inter-branch ‘anti-cooperative’ couplings.}, number={84}, journal={Chemical Communications}, publisher={Royal Society of Chemistry (RSC)}, author={Durand, Nicolas and Mhanna, Rana and Savel, Paul and Akdas-Kiliç, Huriye and Malval, Jean-Pierre and Soppera, Olivier and Fillaut, Jean-Luc}, year={2020}, pages={12801–12804} }
 @article{durand_savel_akdas-kilic_boucekkine_malval_fillaut_2019, title={Polypyridyl Ruthenium Complexes: Versatile Tools for Linear and Non-Linear Optics}, url={http://dx.doi.org/10.1109/icton.2019.8840409}, DOI={10.1109/icton.2019.8840409}, abstractNote={Coordination complexes have been attracting considerable interest due to their potential nonlinear optical (NLO) properties and applications in optoelectronic and photonic devices. Incorporation of metal atoms into ʌ-conjugated systems allows many variables to be adjusted, such as the nature of ligands and metal ions as well as the symmetry of the complexes. In this paper, new ruthenium(II) complexes of formula [Ru(bpy)2(L)][PF6] and [Ru (L)3][PF6]2 are reported. We studied the influence of the nature of ligands, structural features and symmetry of these complexes on their two-photon absorption properties to provide useful physical and chemical insights for similar ruthenium complexes.}, journal={2019 21st International Conference on Transparent Optical Networks (ICTON)}, publisher={IEEE}, author={Durand, Nicolas and Savel, Paul and Akdas-Kilic, Huriye and Boucekkine, Abdou and Malval, Jean-Pierre and Fillaut, Jean-Luc}, year={2019}, month={Jul} }