Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes
Abstract
Herein, we report the synthesis and excited-state dynamics for a series of homoleptic copper(I) trifluoromethylated phenanthroline complexes with two, three, and four trifluoromethyl functional groups. Our analysis of the steady-state absorbance and emission, transient-absorption spectroscopy, and electronic-structure-theory calculations results enable in-depth analysis of the pseudo-Jahn–Teller distortion inhibition from increased steric hindrance of the trifluoromethyl functional group relative to the prototypical dimethyl phenanthroline complex. Surprisingly, our results demonstrate that the greatest degree of pseudo-Jahn–Teller distortion inhibition is achieved with trifluoromethylation of only the 2 and 9 positions by an unusual combination of steric hindrance and stabilization of a nondistorted 1MLCT manifold observed by transient kinetic lifetimes and optimized excited-state structures. The intersystem-crossing (ISC) lifetime for the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex is 69 ps, while the triplet excited-state lifetime and emission quantum yield are 106 ns and 4 × 10–3, respectively. Further trifluoromethylation of the phenanthroline yields a greater σ bond inductive withdrawing force on the phenanthroline nitrogens, ultimately resulting in weaker coordination to the copper. Last, the surprising success of the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex by adjusting both ligand sterics and electronic properties outlines a new strategy for developing long-lived Cu(I) charge-transfer complexes.
- Authors:
-
[1];
[2];
[1]
- Department of Chemistry and Chemical Biology, The University of New Mexico, Albuquerque, New Mexico 87131, United States
- Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1604010
- Report Number(s):
- LA-UR-19-30812
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- 89233218CNA000001; CHE 1602240; CHE 1362302
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 5; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Light absorption; Metal to ligand charge transfer; Absorption; Ligands; Excited states
Citation Formats
Livshits, Maksim Yuryevich, Reeves, Brian J., DeWeerd, Nicholas J., Strauss, Steven H., Boltalina, Olga V., and Rack, Jeffrey J. Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.9b03146.
Livshits, Maksim Yuryevich, Reeves, Brian J., DeWeerd, Nicholas J., Strauss, Steven H., Boltalina, Olga V., & Rack, Jeffrey J. Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes. United States. https://doi.org/10.1021/acs.inorgchem.9b03146
Livshits, Maksim Yuryevich, Reeves, Brian J., DeWeerd, Nicholas J., Strauss, Steven H., Boltalina, Olga V., and Rack, Jeffrey J. Wed .
"Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes". United States. https://doi.org/10.1021/acs.inorgchem.9b03146. https://www.osti.gov/servlets/purl/1604010.
@article{osti_1604010,
title = {Trifluoromethylated Phenanthroline Ligands Reduce Excited-State Distortion in Homoleptic Copper(I) Complexes},
author = {Livshits, Maksim Yuryevich and Reeves, Brian J. and DeWeerd, Nicholas J. and Strauss, Steven H. and Boltalina, Olga V. and Rack, Jeffrey J.},
abstractNote = {Herein, we report the synthesis and excited-state dynamics for a series of homoleptic copper(I) trifluoromethylated phenanthroline complexes with two, three, and four trifluoromethyl functional groups. Our analysis of the steady-state absorbance and emission, transient-absorption spectroscopy, and electronic-structure-theory calculations results enable in-depth analysis of the pseudo-Jahn–Teller distortion inhibition from increased steric hindrance of the trifluoromethyl functional group relative to the prototypical dimethyl phenanthroline complex. Surprisingly, our results demonstrate that the greatest degree of pseudo-Jahn–Teller distortion inhibition is achieved with trifluoromethylation of only the 2 and 9 positions by an unusual combination of steric hindrance and stabilization of a nondistorted 1MLCT manifold observed by transient kinetic lifetimes and optimized excited-state structures. The intersystem-crossing (ISC) lifetime for the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex is 69 ps, while the triplet excited-state lifetime and emission quantum yield are 106 ns and 4 × 10–3, respectively. Further trifluoromethylation of the phenanthroline yields a greater σ bond inductive withdrawing force on the phenanthroline nitrogens, ultimately resulting in weaker coordination to the copper. Last, the surprising success of the 2,9-bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex by adjusting both ligand sterics and electronic properties outlines a new strategy for developing long-lived Cu(I) charge-transfer complexes.},
doi = {10.1021/acs.inorgchem.9b03146},
journal = {Inorganic Chemistry},
number = 5,
volume = 59,
place = {United States},
year = {Wed Feb 12 00:00:00 EST 2020},
month = {Wed Feb 12 00:00:00 EST 2020}
}
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Works referenced in this record:
An element of surprise—efficient copper-functionalized dye-sensitized solar cells
journal, January 2008
- Bessho, Takeru; Constable, Edwin C.; Graetzel, Michael
- Chemical Communications, Issue 32
Thermally activated delayed fluorescence processes for Cu( i ) complexes in solid-state: a computational study using quantitative prediction
journal, January 2018
- Lv, Lingling; Liu, Kui; Yuan, Kun
- RSC Advances, Vol. 8, Issue 50
First application of the HETPHEN concept to new heteroleptic bis(diimine) copper(i) complexes as sensitizers in dye sensitized solar cells
journal, January 2013
- Sandroni, Martina; Kayanuma, Megumi; Planchat, Aurélien
- Dalton Transactions, Vol. 42, Issue 30
Studies of photoinduced electron transfer from bis(2,9-dimethyl-1,10-phenanthroline)copper(I)
journal, August 1978
- Ahn, Byung-Tae; McMillin, David R.
- Inorganic Chemistry, Vol. 17, Issue 8
A light-induced redox reaction of bis(2,9-dimethyl-1,10-phenanthroline)copper(I)
journal, April 1977
- McMillin, David R.; Buckner, Michael T.; Ahn, Byung Tae.
- Inorganic Chemistry, Vol. 16, Issue 4
Photostudies of copper(I) systems. 6. Room-temperature emission and quenching studies of bis(2,9-dimethyl-1,10-phenanthroline)copper(I)
journal, November 1980
- Blaskie, Marcus W.; McMillin, David R.
- Inorganic Chemistry, Vol. 19, Issue 11
Interplays of excited state structures and dynamics in copper(I) diimine complexes: Implications and perspectives
journal, January 2015
- Mara, Michael W.; Fransted, Kelly A.; Chen, Lin X.
- Coordination Chemistry Reviews, Vol. 282-283
Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis
journal, March 2013
- Prier, Christopher K.; Rankic, Danica A.; MacMillan, David W. C.
- Chemical Reviews, Vol. 113, Issue 7
Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices
journal, March 2011
- Wagenknecht, Paul S.; Ford, Peter C.
- Coordination Chemistry Reviews, Vol. 255, Issue 5-6
Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+
journal, July 2015
- Auböck, Gerald; Chergui, Majed
- Nature Chemistry, Vol. 7, Issue 8
An electronic structural model for the emitting MLCT excited states of Ru(bpy)32+ and Os(bpy)32+
journal, November 1984
- Kober, Edward M.; Meyer, Thomas J.
- Inorganic Chemistry, Vol. 23, Issue 24
A combined computational and experimental study of the [Co(bpy)3]2+/3+ complexes as one-electron outer-sphere redox couples in dye-sensitized solar cell electrolyte media
journal, January 2014
- Yaghoobi Nia, Narges; Farahani, Pooria; Sabzyan, Hassan
- Physical Chemistry Chemical Physics, Vol. 16, Issue 23
Flash photolysis and quenching studies of copper(I) systems in the presence of Lewis bases: inorganic exciplexes?
journal, September 1987
- Palmer, Cynthia E. A.; McMillin, David R.; Kirmaier, Christine
- Inorganic Chemistry, Vol. 26, Issue 19
Structure-Dependent Photophysical Properties of Singlet and Triplet Metal-to-Ligand Charge Transfer States in Copper(I) Bis(diimine) Compounds
journal, October 2003
- Siddique, Zainul Abedin; Yamamoto, Yuichi; Ohno, Takeshi
- Inorganic Chemistry, Vol. 42, Issue 20
MLCT State Structure and Dynamics of a Copper(I) Diimine Complex Characterized by Pump−Probe X-ray and Laser Spectroscopies and DFT Calculations
journal, June 2003
- Chen, Lin X.; Shaw, George B.; Novozhilova, Irina
- Journal of the American Chemical Society, Vol. 125, Issue 23
Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis- Phenanthrolines in Solution
journal, February 2007
- Shaw, George B.; Grant, Christian D.; Shirota, Hideaki
- Journal of the American Chemical Society, Vol. 129, Issue 7
Ultrafast structural flattening motion in photoinduced excited state dynamics of a bis(diimine) copper( i ) complex
journal, January 2016
- Du, Likai; Lan, Zhenggang
- Physical Chemistry Chemical Physics, Vol. 18, Issue 11
Ultrafast Excited-State Dynamics of Copper(I) Complexes
journal, February 2015
- Iwamura, Munetaka; Takeuchi, Satoshi; Tahara, Tahei
- Accounts of Chemical Research, Vol. 48, Issue 3
Intriguing Effects of Halogen Substitution on the Photophysical Properties of 2,9-(Bis)halo-Substituted Phenanthrolinecopper(I) Complexes
journal, May 2019
- Brown-Xu, Samantha; Fumanal, Maria; Gourlaouen, Christophe
- Inorganic Chemistry, Vol. 58, Issue 12
New luminescent copper(I) complexes with extended π-conjugation
journal, February 2018
- Soulis, Kévin; Gourlaouen, Christophe; Daniel, Chantal
- Polyhedron, Vol. 140
Steric influences on the photoluminescence from copper(I) phenanthrolines in rigid media
journal, February 1991
- Everly, R. Michael.; Ziessel, Raymond.; Suffert, Jean.
- Inorganic Chemistry, Vol. 30, Issue 3
Charge-transfer absorption and emission of Cu(NN)2+ systems
journal, December 1987
- Ichinaga, Ann K.; Kirchhoff, Jon R.; McMillin, David R.
- Inorganic Chemistry, Vol. 26, Issue 25
Cooperative Substituent Effects on the Excited States of Copper Phenanthrolines
journal, October 1999
- Cunningham, Corey T.; Cunningham, Kurstan L. H.; Michalec, Joseph F.
- Inorganic Chemistry, Vol. 38, Issue 20
Design of a Long-Lifetime, Earth-Abundant, Aqueous Compatible Cu(I) Photosensitizer Using Cooperative Steric Effects
journal, July 2013
- McCusker, Catherine E.; Castellano, Felix N.
- Inorganic Chemistry, Vol. 52, Issue 14
Influence of Ligand Substitution on Excited State Structural Dynamics in Cu(I) Bisphenanthroline Complexes †
journal, November 2010
- Lockard, Jenny V.; Kabehie, Sanaz; Zink, Jeffrey I.
- The Journal of Physical Chemistry B, Vol. 114, Issue 45
The beneficial effects of trifluoromethyl-substituents on the photoconversion efficiency of copper( i ) dyes in dye-sensitized solar cells
journal, January 2015
- Brunner, Fabian; Klein, Y. Maximilian; Keller, Sarah
- RSC Advances, Vol. 5, Issue 72
Electrochemical Characteristics of the Copper(II)-Copper(I) Redox Couple in Dimethyl Sulfoxide Solutions
journal, January 1990
- Benari, Md; Hefter, Gt
- Australian Journal of Chemistry, Vol. 43, Issue 11
A Photoluminescent Copper(I) Complex with an Exceptionally High CuII/CuI Redox Potential: [Cu(bfp)2]+ (bfp=2,9-bis(trifluoromethyl)-1,10-phenanthroline)
journal, June 1998
- Miller, Mark T.; Gantzel, Peter K.; Karpishin, Timothy B.
- Angewandte Chemie International Edition, Vol. 37, Issue 11
Cu (I) (2,9-Bis(trifluoromethyl)-1,10-phenanthroline) 2 + Complexes: Correlation between Solid-State Structure and Photoluminescent Properties
journal, December 2004
- Kovalevsky, Andrey Yu.; Gembicky, Milan; Coppens, Philip
- Inorganic Chemistry, Vol. 43, Issue 26
Trifluoromethyl-substituted 2,2'-bipyridine ligands. Synthetic control of excited-state properties of ruthenium(II) tris-chelate complexes
journal, September 1992
- Furue, Masaoki; Maruyama, Kazunori; Oguni, Tadayoshi
- Inorganic Chemistry, Vol. 31, Issue 18
Syntheses of 2,9-bis(halomethyl-1,10-phenanthrolines: potential robust ligands for metal oxidation catalysts
journal, March 1993
- Beer, Robert H.; Jimenez, Jose; Drago, Russell S.
- The Journal of Organic Chemistry, Vol. 58, Issue 7
Time-resolved resonance Raman spectroscopy of bis(2,9-dimethyl-1,10-phenanthroline)copper(1+) in solution
journal, July 1991
- Gordon, Keith C.; McGarvey, John J.
- Inorganic Chemistry, Vol. 30, Issue 15
Taming Hot CF 3 Radicals: Incrementally Tuned Families of Polyarene Electron Acceptors for Air-Stable Molecular Optoelectronics
journal, March 2013
- Kuvychko, Igor V.; Castro, Karlee P.; Deng, S. H. M.
- Angewandte Chemie International Edition, Vol. 52, Issue 18
Incremental Tuning Up of Fluorous Phenazine Acceptors
journal, January 2016
- Castro, Karlee P.; Clikeman, Tyler T.; DeWeerd, Nicholas J.
- Chemistry - A European Journal, Vol. 22, Issue 12
Solid-State Structure Dependence of the Molecular Distortion and Spectroscopic Properties of the Cu(I) Bis(2,9-dimethyl-1,10-phenanthroline) Ion
journal, December 2003
- Kovalevsky, Andrey Yu.; Gembicky, Milan; Novozhilova, Irina V.
- Inorganic Chemistry, Vol. 42, Issue 26
Transient Absorption Dynamics of Sterically Congested Cu(I) MLCT Excited States
journal, March 2015
- Garakyaraghi, Sofia; Danilov, Evgeny O.; McCusker, Catherine E.
- The Journal of Physical Chemistry A, Vol. 119, Issue 13