{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T04:43:02Z","timestamp":1760244182086,"version":"build-2065373602"},"reference-count":52,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2022,10,17]],"date-time":"2022-10-17T00:00:00Z","timestamp":1665964800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Science and Technology Project of the 14th Five-year Plan of Jilin Provincial Department of Education","award":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"],"award-info":[{"award-number":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"]}]},{"name":"National Key R&amp;D Program of China","award":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"],"award-info":[{"award-number":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"]}]},{"name":"Natural Science Foundation of Science and Technology Department of Jilin Province, China","award":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"],"award-info":[{"award-number":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"]}]},{"DOI":"10.13039\/501100001809","name":"The National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"],"award-info":[{"award-number":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"name":"The 13th Five-year Plan of Jilin Provincial Department of Education","award":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"],"award-info":[{"award-number":["JJKH20220258KJ","2018YFB1501903","20190201228JC","21473071","21173099","20973078","20673045","51673","JJKH20211041KJ"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Cu(I) complexes have received widespread attention as a promising alternative to traditional noble-metal complexes. Herein, we systematically study the properties of Cu(I) complexes from homo- to hetero-ligands, and found the following: (1) hetero-ligands are beneficial to regulate phosphorescent efficiency; (2) when the hetero-ligands in a tetracoordinated Cu(I) complex are 1:1, the ligands coordinate along the dx2-y2 direction of Cu(I) ion, which can observably suppress structural deformation; (3) unlike the P^P ligand, the N^N ligand can enhance the participation of Cu(I) during the transition process; (4) the addition of an appropriate amount of P^P ligand can effectively raise the energy level of HOMO (highest occupied molecular orbital), enhance the proportion of LLCT (ligand\u2013ligand charge transfer), and thereby increase the available singlet emission transition moments which can be borrowed, thus promoting the radiative decay process. As a result, this work provides a detailed understanding of the effects of different ligands in Cu(I) complexes, and provides a valuable reference and theoretical basis for regulating and designing the phosphorescent properties of Cu(I) complexes in the future.<\/jats:p>","DOI":"10.3390\/ma15207253","type":"journal-article","created":{"date-parts":[[2022,10,17]],"date-time":"2022-10-17T21:11:51Z","timestamp":1666041111000},"page":"7253","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["A Theoretical Investigation into the Homo- and Hetero-leptic Cu(I) Phosphorescent Complexes Bearing 2,9-dimethyl-1,10-phenanthroline and bis [2-(diphenylphosphino)phenyl]ether Ligand"],"prefix":"10.3390","volume":"15","author":[{"given":"Lu","family":"Shen","sequence":"first","affiliation":[{"name":"Department of Science, Jilin Jianzhu University, Changchun 130118, China"},{"name":"Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2991-6069","authenticated-orcid":false,"given":"Yu-Yang","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Physics, Northeast Normal University, Changchun 130024, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Teng-Fei","family":"He","sequence":"additional","affiliation":[{"name":"Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lu-Yi","family":"Zou","sequence":"additional","affiliation":[{"name":"Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jing-Fu","family":"Guo","sequence":"additional","affiliation":[{"name":"School of Physics, Northeast Normal University, Changchun 130024, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ai-Min","family":"Ren","sequence":"additional","affiliation":[{"name":"Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,10,17]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"638","DOI":"10.1039\/B916237B","article-title":"Transition-metal phosphors with cyclometalating ligands: Fundamentals and applications","volume":"39","author":"Chi","year":"2010","journal-title":"Chem. Soc. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2763","DOI":"10.1021\/ic9704896","article-title":"Synthesis, Characterization, Absorption Spectra, and Luminescence Properties of Organometallic Platinum(II) Terpyridine Complexes","volume":"37","author":"Arena","year":"1998","journal-title":"Inorg. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3745","DOI":"10.1021\/om0498246","article-title":"Highly Efficient Red Phosphorescent Osmium(II) Complexes for OLED Applications","volume":"23","author":"Tung","year":"2004","journal-title":"Organometallics"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1157","DOI":"10.1021\/ic048538j","article-title":"Synthesis and Characterization of Phenanthrylphosphine Gold Complex:\u2009 Observation of Au-Induced Blue-Green Phosphorescence at Room Temperature","volume":"44","author":"Osawa","year":"2005","journal-title":"Inorg. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1707","DOI":"10.1039\/c2nr11251e","article-title":"Novel hollow mesoporous 1D TiO2 nanofibers as photovoltaic and photocatalytic materials","volume":"4","author":"Zhang","year":"2012","journal-title":"Nanoscale"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3172","DOI":"10.1021\/ac00114a012","article-title":"Oxygen sensors based on luminescence quenching: Interactions of pyrene with the polymer supports","volume":"67","author":"Xu","year":"1995","journal-title":"Anal. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"9561","DOI":"10.1021\/ja00025a021","article-title":"Visible-light photolysis of hydrogen iodide using sensitized layered semiconductor particles","volume":"113","author":"Kim","year":"1991","journal-title":"J. Am. Chem. Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"113","DOI":"10.1016\/0010-8545(90)80041-Q","article-title":"Spectral, photophysical and photochemical properties of Ru(bpy)32+ on porous vycor glass","volume":"104","author":"Gafney","year":"1990","journal-title":"Coord. Chem. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2622","DOI":"10.1016\/j.ccr.2011.01.042","article-title":"The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs","volume":"255","author":"Yersin","year":"2011","journal-title":"Coord. Chem. Rev."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2185","DOI":"10.1039\/b716650h","article-title":"Luminescent complexes beyond the platinum group: The d10 avenue","volume":"19","author":"Barbieri","year":"2008","journal-title":"Chem. Commun."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"8369","DOI":"10.1039\/C4DT02853H","article-title":"Application of three-coordinate copper(I) complexes with halide ligands in organic light-emitting diodes that exhibit delayed fluorescence","volume":"44","author":"Osawa","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"13294","DOI":"10.1039\/C5DT01870F","article-title":"Alkynyl triphosphine copper complexes: Synthesis and photophysical studies","volume":"44","author":"Chakkaradhari","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"8506","DOI":"10.1039\/C4DT02631D","article-title":"A new class of luminescent Cu(I) complexes with tripodal ligands-TADF emitters for the yellow to red color range","volume":"44","author":"Gneuss","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"14628","DOI":"10.1039\/c3dt51288f","article-title":"Heteroleptic diimine copper(I) complexes with large extinction coefficients: Synthesis, quantum chemistry calculations and physico-chemical properties","volume":"42","author":"Sandroni","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4591","DOI":"10.1021\/jp403751m","article-title":"Solvent-Induced Luminescence Quenching: Static and Time-Resolved X-Ray Absorption Spectroscopy of a Copper(I) Phenanthroline Complex","volume":"117","author":"Penfold","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"3077","DOI":"10.1039\/B707398D","article-title":"Electrophosphorescent homo- and heteroleptic copper(i) complexes prepared from various bis-phosphine ligands","volume":"29","author":"Moudam","year":"2007","journal-title":"Chem. Commun."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"12140","DOI":"10.1021\/ic4020042","article-title":"Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands","volume":"52","author":"Kaeser","year":"2013","journal-title":"Inorg. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"6","DOI":"10.1021\/ja012247h","article-title":"Simple Cu(I) Complexes with Unprecedented Excited-State Lifetimes","volume":"124","author":"Cuttell","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2093","DOI":"10.1016\/j.ccr.2006.02.007","article-title":"Coordination complexes exhibiting room-temperature phosphorescence: Evaluation of their suitability as triplet emitters in organic light emitting diodes","volume":"250","author":"Evans","year":"2006","journal-title":"Coord. Chem. Rev."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"608","DOI":"10.1039\/C7DT03682E","article-title":"The coordination- and photochemistry of copper(i) complexes: Variation of N^N ligands from imidazole to tetrazole","volume":"47","author":"Bergmann","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"997","DOI":"10.1039\/C2DT32056H","article-title":"New tetrazole-based Cu(i) homo- and heteroleptic complexes with various P^P ligands: Synthesis, characterization, redox and photophysical properties","volume":"42","author":"Femoni","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4444","DOI":"10.1039\/b608641a","article-title":"A series of luminescent Cu(i) mixed-ligand complexes containing 2,9-dimethyl-1,10-phenanthroline and simple diphosphine ligands","volume":"37","author":"Saito","year":"2006","journal-title":"Dalton Trans."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4143","DOI":"10.1039\/c3cp54322f","article-title":"Substituent effect on the photoinduced structural change of Cu(i) complexes observed by femtosecond emission spectroscopy","volume":"16","author":"Iwamura","year":"2014","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2336","DOI":"10.1021\/jacs.7b12671","article-title":"Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes","volume":"140","author":"Mohankumar","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Fox, Gaussian 09, Revision A.02, Gaussian Inc."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"997","DOI":"10.1103\/PhysRevLett.52.997","article-title":"Density-Functional Theory for Time-Dependent Systems","volume":"52","author":"Runge","year":"1984","journal-title":"Phys. Rev. Lett."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"5202","DOI":"10.1021\/j100270a017","article-title":"Ab initio calculations including relativistic effects for diatomic silver, diatomic gold, silver-gold (AgAu), silver hydride (AgH), and gold hydride (AuH)","volume":"89","author":"Ross","year":"1985","journal-title":"J. Phys. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"209","DOI":"10.1080\/00268977400100171","article-title":"Accuracy of AH n equilibrium geometries by single determinant molecular orbital theory","volume":"27","author":"Hariharan","year":"1974","journal-title":"Mol. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2999","DOI":"10.1021\/cr9904009","article-title":"Quantum Mechanical Continuum Solvation Models","volume":"105","author":"Tomasi","year":"2005","journal-title":"Chem. Rev."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"581","DOI":"10.1063\/1.1477925","article-title":"Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules","volume":"117","author":"Autschbach","year":"2002","journal-title":"J. Chem. Phys."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"3872","DOI":"10.1021\/ct400415r","article-title":"Computational Prediction for Singlet- and Triplet-Transition Energies of Charge-Transfer Compounds","volume":"9","author":"Huang","year":"2013","journal-title":"J. Chem. Theory Comput."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-functional exchange-energy approximation with correct asymptotic behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"11127","DOI":"10.1021\/jp0539223","article-title":"Density Functionals for Inorganometallic and Organometallic Chemistry","volume":"109","author":"Schultz","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"12129","DOI":"10.1063\/1.1626543","article-title":"Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes","volume":"119","author":"Staroverov","year":"2003","journal-title":"J. Chem. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"48","DOI":"10.1007\/s00214-001-0300-3","article-title":"Reparameterization of hybrid functionals based on energy differences of states of different multiplicity","volume":"107","author":"Reiher","year":"2001","journal-title":"Theor. Chem. Acc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"3865","DOI":"10.1103\/PhysRevLett.77.3865","article-title":"Generalized Gradient Approximation Made Simple","volume":"77","author":"Perdew","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"152","DOI":"10.1016\/S0009-2614(99)01113-6","article-title":"Accurate excitation energies from time-dependent density functional theory: Assessing the PBE0 model for organic free radicals","volume":"314","author":"Adamo","year":"1999","journal-title":"Chem. Phys. Lett."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"3405","DOI":"10.1063\/1.1774975","article-title":"Development of density functionals for thermochemical kinetics","volume":"121","author":"Boese","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"525","DOI":"10.1007\/s00214-007-0401-8","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06 functionals and 12 other functionals","volume":"119","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1073","DOI":"10.3866\/PKU.WHXB20031118","article-title":"Average van der Waals Radii of Atoms in Crystals","volume":"19","year":"2003","journal-title":"Acta Phys. Chim. Sin."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"6535","DOI":"10.1021\/ic7005474","article-title":"Copper(I) Complexes of Bis(2-(diphenylphosphino)phenyl) Ether:\u2009 Synthesis, Reactivity, and Theoretical Calculations","volume":"46","author":"Venkateswaran","year":"2007","journal-title":"Inorg. Chem."},{"key":"ref_43","unstructured":"(The PyMOL Molecular Graphics System, 2010). The PyMOL Molecular Graphics System, Version 1.6.0.0."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"913","DOI":"10.1063\/1.98799","article-title":"Organic electroluminescent diodes","volume":"51","author":"Tang","year":"1987","journal-title":"Appl. Phys. Lett."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"9388","DOI":"10.1039\/b916782j","article-title":"Novel luminescent iminephosphine complex of copper(i) with high photochemical and electrochemical stability","volume":"43","author":"Qin","year":"2009","journal-title":"Dalton Trans."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"7176","DOI":"10.1039\/C4CC02037E","article-title":"Control of emission colour with N-heterocyclic carbene (NHC) ligands in phosphorescent three-coordinate Cu(i) complexes","volume":"50","author":"Krylova","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"6366","DOI":"10.1021\/ic034412v","article-title":"Structure-Dependent Photophysical Properties of Singlet and Triplet Metal-to-Ligand Charge Transfer States in Copper(I) Bis(diimine) Compounds","volume":"42","author":"Siddique","year":"2003","journal-title":"Inorg. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1007\/s002140050207","article-title":"The Beijing four-component density functional program package (BDF) and its application to EuO, EuS, YbO and YbS","volume":"96","author":"Liu","year":"1997","journal-title":"Theor. Chem. Acc."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"257","DOI":"10.1142\/S0219633603000471","article-title":"The Beijing Density Functional (BDF) Program Package: Methodologies and Applications","volume":"2","author":"Liu","year":"2003","journal-title":"J. Theor. Comput. Chem."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"10341","DOI":"10.1021\/jp035717y","article-title":"Influence of Frequency Shifts on Electron Transfer Processes","volume":"107","author":"Freed","year":"2003","journal-title":"J. Phys. Chem. B"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"6433","DOI":"10.1002\/chem.201304375","article-title":"A Theoretical Investigation into the Luminescent Properties of d8-Transition-Metal Complexes with Tetradentate Schiff Base Ligands","volume":"20","author":"Tong","year":"2014","journal-title":"Chem. A Eur. J."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"209","DOI":"10.1080\/02603598708072291","article-title":"Rate-Constant Expressions for Nonadiabatic Electron-Transfer Reactions","volume":"6","author":"Brunschwig","year":"1987","journal-title":"Comments Inorg. Chem."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/15\/20\/7253\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T00:56:00Z","timestamp":1760144160000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/15\/20\/7253"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,10,17]]},"references-count":52,"journal-issue":{"issue":"20","published-online":{"date-parts":[[2022,10]]}},"alternative-id":["ma15207253"],"URL":"https:\/\/doi.org\/10.3390\/ma15207253","relation":{},"ISSN":["1996-1944"],"issn-type":[{"type":"electronic","value":"1996-1944"}],"subject":[],"published":{"date-parts":[[2022,10,17]]}}}