Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

Xie, Zhu‐Lin; Liu, Xiaolin; Valentine, Andrew J. S.; Lynch, Vincent M.; Tiede, David M.; Li, Xiaosong; Mulfort, Karen L.

doi:10.1002/ange.202111764

Title: Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

Journal Article · 15 December 2021 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202111764 · OSTI ID:1835938

^[1];

^[2]; Valentine, Andrew J. S. ^[2]; Lynch, Vincent M. ^[3];

^[1];

^[2];

^[1]

Division of Chemical Sciences and Engineering Argonne National Laboratory 9700 S Cass Ave Lemont IL 60439 USA
Department of Chemistry University of Washington 109 Bagley Hall Seattle WA 98195-1700 USA
Department of Chemistry University of Texas at Austin 105 E 24TH ST. Austin TX 78712-1224 USA

Abstract High‐energy X‐ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long‐range order, but is underutilized for molecular complexes in solution. We demonstrate the application of HEXS/PDF with 0.26 Å resolution to uncover the solution structure of five bimetallic Cu ^I /Ru ^II /Os ^II complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metal⋅⋅⋅metal distances separated by over 12 Å. The metal⋅⋅⋅metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub‐Ångström conformational differences by direct comparison of solution phase and solid‐state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1835938

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 5 Vol. 134; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (62)

New Sterically Encumbered 2,9-Diarylphenanthrolines for the Selective Formation of Heteroleptic Bis(phenanthroline)copper(I) Complexes Schmittel, Michael; Michel, Christoph; Liu, Shi-Xia European Journal of Inorganic Chemistry, Vol. 2001, Issue 5 https://doi.org/10.1002/1099-0682(200105)2001:5<1155::AID-EJIC1155>3.0.CO;2-C	journal	May 2001
Steric Effects in the Self‐Assembly of Palladium Complexes with Chelating Diamine Ligands Holló‐Sitkei, Eszter; Tárkányi, Gábor; Párkányi, László European Journal of Inorganic Chemistry, Vol. 2008, Issue 10 https://doi.org/10.1002/ejic.200701189	journal	March 2008
Determination of actinide speciation in solution using high-energy X-ray scattering Soderholm, L.; Skanthakumar, S.; Neuefeind, J. Analytical and Bioanalytical Chemistry, Vol. 383, Issue 1 https://doi.org/10.1007/s00216-005-3322-1	journal	July 2005
X-ray scattering combined with coordinate-based analyses for applications in natural and artificial photosynthesis Tiede, David M.; Mardis, Kristy L.; Zuo, Xiaobing Photosynthesis Research, Vol. 102, Issue 2-3 https://doi.org/10.1007/s11120-009-9475-6	journal	July 2009
Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects Miertuš, S.; Scrocco, E.; Tomasi, J. Chemical Physics, Vol. 55, Issue 1 https://doi.org/10.1016/0301-0104(81)85090-2	journal	February 1981
Electron and energy transfer from CuI MLCT excited states Ruthkosky, Mark; Kelly, Craig A.; Castellano, Felix N. Coordination Chemistry Reviews, Vol. 171 https://doi.org/10.1016/S0010-8545(98)90045-5	journal	April 1998
Interplays of excited state structures and dynamics in copper(I) diimine complexes: Implications and perspectives Mara, Michael W.; Fransted, Kelly A.; Chen, Lin X. Coordination Chemistry Reviews, Vol. 282-283 https://doi.org/10.1016/j.ccr.2014.06.013	journal	January 2015
Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes Zheng, Jiaxin; Tan, Guoyu; Shan, Peng Chem, Vol. 4, Issue 12 https://doi.org/10.1016/j.chempr.2018.09.004	journal	December 2018
Bridging the solution divide: comprehensive structural analyses of dynamic RNA, DNA, and protein assemblies by small-angle X-ray scattering Rambo, Robert P.; Tainer, John A. Current Opinion in Structural Biology, Vol. 20, Issue 1 https://doi.org/10.1016/j.sbi.2009.12.015	journal	February 2010
Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E. Chemistry of Materials, Vol. 27, Issue 13 https://doi.org/10.1021/acs.chemmater.5b01560	journal	June 2015
Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation Knope, Karah E.; Skanthakumar, S.; Soderholm, L. Inorganic Chemistry, Vol. 54, Issue 21 https://doi.org/10.1021/acs.inorgchem.5b01242	journal	October 2015
Comparative CHARMM and AMOEBA Simulations of Lanthanide Hydration Energetics and Experimental Aqueous-Solution Structures Qiao, Baofu; Skanthakumar, S.; Soderholm, L. Journal of Chemical Theory and Computation, Vol. 14, Issue 3 https://doi.org/10.1021/acs.jctc.7b01018	journal	February 2018
Linking Solution Structures and Energetics: Thorium Nitrate Complexes Skanthakumar, S.; Jin, Geng Bang; Lin, Jian The Journal of Physical Chemistry B, Vol. 121, Issue 36 https://doi.org/10.1021/acs.jpcb.7b06567	journal	August 2017
Understanding Structure, Metal Distribution, and Water Adsorption in Mixed-Metal MOF-74 Howe, Joshua D.; Morelock, Cody R.; Jiao, Yang The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b11719	journal	December 2016
Long-Range Ion-Ordering in Salt-Concentrated Lithium-Ion Battery Electrolytes: A Combined High-Energy X-ray Total Scattering and Molecular Dynamics Simulation Study Fujii, Kenta; Matsugami, Masaru; Ueno, Kazuhide The Journal of Physical Chemistry C, Vol. 121, Issue 41 https://doi.org/10.1021/acs.jpcc.7b08243	journal	October 2017
Domain Structures of Ni and NiFe (Oxy)Hydroxide Oxygen-Evolution Catalysts from X-ray Pair Distribution Function Analysis Batchellor, Adam S.; Kwon, Gihan; Laskowski, Forrest A. L. The Journal of Physical Chemistry C, Vol. 121, Issue 45 https://doi.org/10.1021/acs.jpcc.7b10306	journal	November 2017
Resolving the Atomic Structure of Sequential Infiltration Synthesis Derived Inorganic Clusters He, Xiang; Waldman, Ruben Z.; Mandia, David J. ACS Nano, Vol. 14, Issue 11 https://doi.org/10.1021/acsnano.0c03848	journal	November 2020
Small-Angle X-ray Scattering of Polymers Chu, Benjamin; Hsiao, Benjamin S. Chemical Reviews, Vol. 101, Issue 6 https://doi.org/10.1021/cr9900376	journal	June 2001
π-Stacking Induced NMR Spectrum Splitting in Enantiomerically Enriched Ru(II) Complexes: Evaluation of Enantiomeric Excess Bergman, Sheba D.; Kol, Moshe Inorganic Chemistry, Vol. 44, Issue 6 https://doi.org/10.1021/ic048569e	journal	January 2005
Photostudies of copper(I) systems. 6. Room-temperature emission and quenching studies of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) Blaskie, Marcus W.; McMillin, David R. Inorganic Chemistry, Vol. 19, Issue 11 https://doi.org/10.1021/ic50213a062	journal	November 1980
Mononuclear and Binuclear Tetrapyrido[3,2- a :2‘,3‘- c :3‘‘,2‘‘- h :2‘‘‘,3‘‘‘- j ]phenazine (tpphz) Ruthenium and Osmium Complexes Bolger, Joseph; Gourdon, André; Ishow, Eléna Inorganic Chemistry, Vol. 35, Issue 10 https://doi.org/10.1021/ic951436w	journal	January 1996
Photophysics of Dinuclear Ru(II) and Os(II) Complexes Based on the Tetrapyrido[3,2- a :2‘,3‘- c :3‘ ‘,2‘ ‘- h :2‘ ‘‘-3‘ ‘‘- j ]phenazine (tpphz) Bridging Ligand Chiorboli, Claudio; Bignozzi, Carlo Alberto; Scandola, Franco Inorganic Chemistry, Vol. 38, Issue 10 https://doi.org/10.1021/ic981284f	journal	May 1999
Cooperative Substituent Effects on the Excited States of Copper Phenanthrolines Cunningham, Corey T.; Cunningham, Kurstan L. H.; Michalec, Joseph F. Inorganic Chemistry, Vol. 38, Issue 20 https://doi.org/10.1021/ic9906611	journal	October 1999
Rapid Excited-State Structural Reorganization Captured by Pulsed X-rays Chen, Lin X.; Jennings, Guy; Liu, Tao Journal of the American Chemical Society, Vol. 124, Issue 36 https://doi.org/10.1021/ja017214g	journal	September 2002
Ultrafast Processes in Bimetallic Dyads with Extended Aromatic Bridges. Energy and Electron Transfer Pathways in Tetrapyridophenazine-Bridged Complexes Chiorboli, Claudio; Rodgers, Michael A. J.; Scandola, Franco Journal of the American Chemical Society, Vol. 125, Issue 2 https://doi.org/10.1021/ja0284916	journal	January 2003
Combining Light-Harvesting and Charge Separation in a Self-Assembled Artificial Photosynthetic System Based on Perylenediimide Chromophores Rybtchinski, Boris; Sinks, Louise E.; Wasielewski, Michael R. Journal of the American Chemical Society, Vol. 126, Issue 39 https://doi.org/10.1021/ja0460514	journal	October 2004
Structural Characterization of Modular Supramolecular Architectures in Solution Tiede, David M.; Zhang, Ruitian; Chen, Lin X. Journal of the American Chemical Society, Vol. 126, Issue 43 https://doi.org/10.1021/ja048209q	journal	November 2004
X-ray Diffraction and DOSY NMR Characterization of Self-Assembled Supramolecular Metallocyclic Species in Solution Megyes, Tünde; Jude, Hershel; Grósz, Tamás Journal of the American Chemical Society, Vol. 127, Issue 30 https://doi.org/10.1021/ja0523690	journal	August 2005
Synthesis and Solution- and Solid-State Characterization of Gold(I) Rings with Short Au···Au Interactions. Spontaneous Resolution of a Gold(I) Complex Deák, Andrea; Megyes, Tünde; Tárkányi, Gábor Journal of the American Chemical Society, Vol. 128, Issue 39 https://doi.org/10.1021/ja064609x	journal	September 2006
Solution-Phase Structural Characterization of Supramolecular Assemblies by Molecular Diffraction O'Donnell, Jodi L.; Zuo, Xiaobing; Goshe, Andrew J. Journal of the American Chemical Society, Vol. 129, Issue 6 https://doi.org/10.1021/ja0659065	journal	February 2007
Solution-Phase Structure of an Artificial Foldamer: X-ray Scattering Study Kelley, Richard F.; Rybtchinski, Boris; Stone, Matthew T. Journal of the American Chemical Society, Vol. 129, Issue 14 https://doi.org/10.1021/ja068213x	journal	April 2007
Coordinative Self-Assembly and Solution-Phase X-ray Structural Characterization of Cavity-Tailored Porphyrin Boxes Lee, Suk Joong; Mulfort, Karen L.; Zuo, Xiaobing Journal of the American Chemical Society, Vol. 130, Issue 3 https://doi.org/10.1021/ja077661h	journal	December 2007
Elucidating the Domain Structure of the Cobalt Oxide Water Splitting Catalyst by X-ray Pair Distribution Function Analysis Du, Pingwu; Kokhan, Oleksandr; Chapman, Karena W. Journal of the American Chemical Society, Vol. 134, Issue 27 https://doi.org/10.1021/ja303826a	journal	June 2012
Complete Structural Characterization of Metallacyclic Complexes in Solution-Phase Using Simultaneously X-ray Diffraction and Molecular Dynamics Simulation Megyes, Tünde; Bálint, Szabolcs; Bakó, Imre Journal of the American Chemical Society, Vol. 130, Issue 29 https://doi.org/10.1021/ja802793g	journal	June 2008
Photoinitiated Charge Transport through π-Stacked Electron Conduits in Supramolecular Ordered Assemblies of Donor−Acceptor Triads Bullock, Joseph E.; Carmieli, Raanan; Mickley, Sarah M. Journal of the American Chemical Society, Vol. 131, Issue 33 https://doi.org/10.1021/ja903903q	journal	August 2009
Resolution of Electronic and Structural Factors Underlying Oxygen-Evolving Performance in Amorphous Cobalt Oxide Catalysts Kwon, Gihan; Jang, Hoyoung; Lee, Jun-Sik Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b02719	journal	July 2018
Structural Investigation into the Threading Intercalation of a Chiral Dinuclear Ruthenium(II) Polypyridyl Complex through a B-DNA Oligonucleotide Fairbanks, Simon D.; Robertson, Craig C.; Keene, F. Richard Journal of the American Chemical Society, Vol. 141, Issue 11 https://doi.org/10.1021/jacs.8b12280	journal	February 2019
Supramolecular Cobaloxime Assemblies for H ₂ Photocatalysis: An Initial Solution State Structure−Function Analysis ^† Mulfort, Karen L.; Tiede, David M. The Journal of Physical Chemistry B, Vol. 114, Issue 45 https://doi.org/10.1021/jp1023636	journal	November 2010
Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses Canton, Sophie E.; Kjær, Kasper S.; Vankó, György Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7359	journal	March 2015
Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer Biasin, Elisa; Fox, Zachary W.; Andersen, Amity Nature Chemistry, Vol. 13, Issue 4 https://doi.org/10.1038/s41557-020-00629-3	journal	February 2021
A molecular cross-linking approach for hybrid metal oxides Jung, Dahee; Saleh, Liban M. A.; Berkson, Zachariah J. Nature Materials, Vol. 17, Issue 4 https://doi.org/10.1038/s41563-018-0021-9	journal	March 2018
Structural variation in copper( i ) complexes with pyridylmethylamide ligands: structural analysis with a new four-coordinate geometry index, τ ₄ Yang, Lei; Powell, Douglas R.; Houser, Robert P. Dalton Trans., Issue 9 https://doi.org/10.1039/B617136B	journal	January 2007
Structure–function analyses of solar fuelscatalysts using in situ X-ray scattering Mulfort, Karen L.; Mukherjee, Anusree; Kokhan, Oleksandr Chem. Soc. Rev., Vol. 42, Issue 6 https://doi.org/10.1039/C2CS35247H	journal	January 2013
Domain structure for an amorphous iridium-oxide water-oxidation catalyst characterized by X-ray pair distribution function analysis Huang, Jier; Blakemore, James D.; Fazi, Diego Phys. Chem. Chem. Phys., Vol. 16, Issue 5 https://doi.org/10.1039/C3CP54878C	journal	January 2014
Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores Kohler, Lars; Hayes, Dugan; Hong, Jiyun Dalton Transactions, Vol. 45, Issue 24 https://doi.org/10.1039/C6DT00324A	journal	January 2016
Synthesis, structure, and excited state kinetics of heteroleptic Cu( i ) complexes with a new sterically demanding phenanthroline ligand Kohler, Lars; Hadt, Ryan G.; Hayes, Dugan Dalton Trans., Vol. 46, Issue 38 https://doi.org/10.1039/C7DT02476B	journal	January 2017
Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000 Platero-Prats, Ana E.; Li, Zhanyong; Gallington, Leighanne C. Faraday Discussions, Vol. 201 https://doi.org/10.1039/C7FD00110J	journal	January 2017
Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy Hayes, Dugan; Kohler, Lars; Hadt, Ryan G. Chemical Science, Vol. 9, Issue 4 https://doi.org/10.1039/C7SC04055E	journal	January 2018
Characterizing electronic and atomic structures for amorphous and molecular metal oxide catalysts at functional interfaces by combining soft X-ray spectroscopy and high-energy X-ray scattering Tiede, David M.; Kwon, Gihan; He, Xiang Nanoscale, Vol. 12, Issue 25 https://doi.org/10.1039/D0NR02350G	journal	January 2020
Stable mixed phenanthroline copper(i) complexes. Key building blocks for supramolecular coordination chemistry Schmittel, Michael; Ganz, Andrea Chemical Communications, Issue 11 https://doi.org/10.1039/a701509g	journal	January 1997
Supramolecular porphyrinic prisms: coordinative assembly and solution phase X-ray structural characterization Lee, Suk Joong; Mulfort, Karen L.; O'Donnell, Jodi L. Chemical Communications, Issue 44 https://doi.org/10.1039/b610025b	journal	January 2006
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008
Metal-coordination-driven dynamic heteroleptic architectures De, Soumen; Mahata, Kingsuk; Schmittel, Michael Chemical Society Reviews, Vol. 39, Issue 5 https://doi.org/10.1039/b922293f	journal	January 2010
Atomic pair distribution functions analysis of disordered low-Z materials Petkov, V.; Ren, Y.; Kabekkodu, S. Physical Chemistry Chemical Physics, Vol. 15, Issue 22 https://doi.org/10.1039/c2cp43378h	journal	January 2013
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg Hay, P. Jeffrey; Wadt, Willard R. The Journal of Chemical Physics, Vol. 82, Issue 1 https://doi.org/10.1063/1.448799	journal	January 1985
X-ray diffraction "fingerprinting" of DNA structure in solution for quantitative evaluation of molecular dynamics simulation Zuo, X.; Cui, G.; Merz, K. M. Proceedings of the National Academy of Sciences, Vol. 103, Issue 10 https://doi.org/10.1073/pnas.0600022103	journal	February 2006
X-Ray Scattering Methods for the Study of Polymer Interfaces Foster, Mark D. Critical Reviews in Analytical Chemistry, Vol. 24, Issue 3 https://doi.org/10.1080/10408349308050553	journal	January 1993
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L. Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678 https://doi.org/10.1107/S0021889804011744	journal	July 2004
Oxyanion induced variations in domain structure for amorphous cobalt oxide oxygen evolving catalysts, resolved by X-ray pair distribution function analysis Kwon, Gihan; Kokhan, Oleksandr; Han, Ali Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 71, Issue 6 https://doi.org/10.1107/S2052520615022180	journal	December 2015
Observing structural reorientations at solvent–nanoparticle interfaces by X-ray diffraction – putting water in the spotlight Zobel, Mirijam Acta Crystallographica Section A Foundations and Advances, Vol. 72, Issue 6 https://doi.org/10.1107/S2053273316013516	journal	October 2016
Universal solvent restructuring induced by colloidal nanoparticles Zobel, M.; Neder, R. B.; Kimber, S. A. J. Science, Vol. 347, Issue 6219 https://doi.org/10.1126/science.1261412	journal	January 2015
Small-Angle X-Ray Scattering from RNA, Proteins, and Protein Complexes Lipfert, Jan; Doniach, Sebastian Annual Review of Biophysics and Biomolecular Structure, Vol. 36, Issue 1 https://doi.org/10.1146/annurev.biophys.36.040306.132655	journal	June 2007

Similar Records

Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

Journal Article · 2021 · Angewandte Chemie (International Edition) · OSTI ID:1869932

Xie, Zhu‐Lin; Liu, Xiaolin; Valentine, Andrew J. S.; +4 more

Polypyridyl-hydrido complexes of osmium(II) and ruthenium(II)

Technical Report · 1982 · OSTI ID:5694626

Caspar, J V; Sullivan, B P; Meyer, T J

Polypyridyl hydrido complexes of osmium(II) and ruthenium(II)

Journal Article · 1983 · Organometallics; (United States) · OSTI ID:6436845

Caspar, J V; Sullivan, B P; Meyer, T J

Title: Bimetallic Copper/Ruthenium/Osmium Complexes: Observation of Conformational Differences Between the Solution Phase and Solid State by Atomic Pair Distribution Function Analysis

Citation Formats

References (62)

Similar Records

Related Subjects