Transcript Supporting Information

Tuning the luminescent properties of a Ag/Au
tetranuclear
complex
featuring
metallophilic
interactions via solvent dependent structural
isomerization.
Rocío Donamaría,† M. Concepción Gimeno,‡ Vito Lippolis,*§ José M. López-deLuzuriaga,*† Miguel Monge,† M. Elena Olmos*†
†
Departamento de Química, Universidad de La Rioja. Centro de investigación de Síntesis Química
(CISQ). Complejo Científico-Tecnológico, 26004-Logroño, SPAIN.
‡
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea
(ISQCH), CSIC-Universidad de Zaragoza, E-50009 Zaragoza, Spain.
§
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio
per Sestu, 09042 Monse-rrato (CA), ITALY.
Supporting Information
Fig S1. Representation of the frontier MOs (HOMO, HOMO-2 and LUMO) for model
systems 1-S0 and 2-S0. Red and green shading distinguishes the positive and negative
phases of the MOs, respectively.
Table S1. Single-point energy calculations for model systems 1-S0 and 2-S0 introducing
dichloromethane as solvent (PCM approach).
Model
Energy (a.u.) in dichloromethane
1-S0 (E-isomer)
-1145.5269
2-S0 (Z-isomer)
-1145.5274
XYZ COORDINATES OF OPTIMIZED STRUCTURES FOR COMPLEXES 1
AND 2 IN THE GROUND AND LOWEST TRIPLET EXCITED STATE
1-S0 xyz-coordinates
S
-4.487100 -2.132000 -2.968200
C
-6.222500 -1.684900 -3.303700
H -6.867700 -2.484400 -2.911000
H -6.360500 -1.683300 -4.396200
C
-6.655400 -0.323200 -2.775200
H -6.065600 0.480900 -3.243700
H -7.705500 -0.149700 -3.059400
S
-6.473300 0.017000 -0.998200
C
-7.409900 -1.344400 -0.225800
H -7.766300 -2.013900 -1.023000
H -8.308300 -0.903700 0.233900
C
-6.663600 -2.119100 0.853100
H -6.370900 -1.448400 1.677300
H -7.346500 -2.870900 1.280800
S
-5.093000 -2.929500 0.425300
C
-5.532700 -3.964000 -1.009700
H -6.588600 -3.784100 -1.261300
H -5.464300 -5.016500 -0.693100
C
-4.632200 -3.787800 -2.225700
H -3.584900 -4.030800 -1.980100
H -4.950600 -4.491200 -3.011500
Ag -3.947000 -0.805600 -0.756200
Au -1.562500 -0.724500 0.538500
C
-0.687000 -2.541500 0.963900
C
-0.335600 -2.902600 2.271100
C
-0.486600 -3.523000 -0.012200
C
0.222200 -4.147200 2.595300
C
0.054800 -4.785600 0.265500
C
0.418100 -5.096600 1.582400
C
-2.627200 1.046800 0.145400
C
-2.357400 1.863000 -0.967700
C
-3.431100 1.621700 1.146700
C
-2.801200 3.188800 -1.062000
C
-3.901900 2.938200 1.086500
C
-3.566700 3.731900 -0.020600
Cl -0.616500 -1.771000 3.557500
Cl
0.654600 -4.533500 4.215100
Cl
1.090300 -6.634600 1.953800
Cl -3.889400 0.654700 2.517800
Cl -4.889500 3.590900 2.333400
Cl -4.111000 5.356400 -0.110700
Cl
0.275100 -5.956000 -0.979900
Cl -0.933300 -3.182800 -1.665900
Cl -1.444800 1.209400 -2.288300
Cl -2.425900 4.154200 -2.434800
S
C
H
H
C
H
H
S
C
H
H
C
H
H
S
C
H
H
C
H
H
Ag
Au
C
C
C
C
C
C
C
C
C
C
C
C
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
5.393000
7.079200
7.637900
7.575900
7.156200
6.683100
8.215300
6.337500
7.103000
7.779600
7.737300
6.127600
5.502100
6.705100
4.895600
5.908900
6.960900
5.853200
5.463200
4.429900
6.108000
3.991400
1.346500
0.693400
0.941800
0.045000
0.552900
-0.385400
-0.129300
2.295300
2.323800
2.834200
2.831400
3.352000
3.346200
1.789400
0.905500
-0.636700
2.894300
4.002500
3.993300
-1.215000
-0.226800
1.727400
2.848100
2.159200
1.498800
2.187000
1.529300
0.068300
-0.629400
-0.227000
-0.330800
0.849500
1.502200
0.268400
1.664900
1.000900
2.296100
2.701800
3.735200
3.427200
4.770800
3.741600
4.114300
4.431200
0.814100
0.717300
2.645600
3.685700
3.014500
5.013200
4.323100
5.330900
-1.102500
-1.671400
-1.892300
-2.952900
-3.175600
-3.709900
3.342000
6.255900
6.946100
-1.245400
-4.097400
-5.273200
4.712000
1.804200
-0.748200
-3.601100
-2.267400
-2.053500
-1.402300
-3.035900
-1.533900
-2.243300
-1.462800
0.040300
1.201700
0.630700
1.889000
2.041300
2.659600
2.735800
1.196400
0.087800
0.185800
0.458000
-1.369200
-1.463300
-1.937000
-0.488700
0.013300
0.371800
-0.531200
1.557500
-0.304100
1.818000
0.877600
-0.373400
-1.658500
0.657300
-1.912600
0.446100
-0.850900
-2.019900
-1.444800
1.178000
2.269200
1.744000
-1.139600
3.274700
2.769500
-3.001800
-3.505900
1-T1 xyz-coordinates
S
-4.453700 -2.462600 -2.294000
C
-6.252500 -2.270800 -2.522900
H
H
C
H
H
S
C
H
H
C
H
H
S
C
H
H
C
H
H
Ag
Au
C
C
C
C
C
C
C
C
C
C
C
C
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Ag
Au
C
C
C
C
C
-6.765900
-6.479500
-6.796700
-6.341200
-7.880000
-6.513000
-7.225800
-7.552300
-8.136500
-6.318900
-6.076200
-6.863300
-4.681900
-5.084000
-6.173400
-4.834000
-4.337000
-3.250300
-4.654900
-3.917000
-1.259300
-0.569400
-0.330400
-0.396700
0.104200
0.023500
0.288600
-2.367800
-2.418000
-2.879900
-2.925500
-3.385300
-3.410600
-0.618300
0.394500
0.821900
-2.908400
-3.987500
-4.044300
0.206000
-0.772200
-1.842900
-2.980400
3.916900
1.250500
0.558400
0.386400
0.319200
-0.038700
-0.116900
-3.059100 -1.952600
-2.458700 -3.584300
-0.893100 -2.168700
-0.118200 -2.805900
-0.869300 -2.368100
-0.259900 -0.484900
-1.576600 0.558600
-2.393800 -0.101500
-1.169200 1.024500
-2.095200 1.666600
-1.290700 2.379400
-2.866200 2.235500
-2.747300 1.218000
-4.059500 0.015500
-4.063100 -0.139800
-5.022100 0.488500
-3.986100 -1.310100
-4.094700 -1.165000
-4.832400 -1.939900
-0.704400 -0.315800
-0.552200 0.216700
-2.424100 0.712200
-2.817700 2.035900
-3.412100 -0.264800
-4.105800 2.374400
-4.713800 0.032000
-5.061800 1.364200
1.138600 -0.299800
1.651500 -1.625400
2.010800 0.701200
2.912200 -1.935200
3.278300 0.425500
3.741200 -0.905100
-1.676300 3.306000
-4.536600 4.014400
-6.648400 1.755300
1.440300 2.338300
4.285200 1.684200
5.292600 -1.268200
-5.889800 -1.213800
-3.022300 -1.920600
0.645300 -2.910900
3.467400 -3.563800
0.704800 -0.291900
0.565200 0.216000
2.438000 0.705600
3.425200 -0.271900
2.833700 2.028400
4.725900 0.022000
4.121500 2.365400
C
C
C
C
C
C
C
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
S
C
H
H
C
H
H
S
C
H
H
C
H
H
S
C
H
H
C
H
H
-0.304300
2.356400
2.405800
2.867400
2.916600
3.374800
3.403100
0.764600
-0.230400
-0.842100
2.892100
3.975400
4.041500
-0.405900
0.610700
1.822100
2.971900
4.720400
6.532100
6.972000
6.891300
7.021000
6.648000
8.120700
6.520500
7.106700
7.519900
7.948500
6.070100
5.732700
6.542100
4.508500
5.069500
6.169300
4.777900
4.481600
3.383800
4.865100
5.075200
-1.127100
-1.636600
-2.002400
-2.895000
-3.268300
-3.726100
3.035500
5.897700
6.660800
-1.437500
-4.279500
-5.274800
4.554600
1.694800
-0.631200
-3.445700
2.116200
1.918600
2.798600
1.933700
0.627000
-0.249200
0.589900
0.272900
1.749400
2.455300
1.434100
2.425200
1.741100
3.284500
2.975200
4.074300
4.058200
5.100200
3.774700
3.876500
4.517700
1.353700
-0.297000
-1.624300
0.702200
-1.937700
0.422600
-0.909800
-1.928100
-1.226100
1.742500
2.341000
1.678600
-1.277900
4.005100
3.300700
-2.905500
-3.567800
-2.456500
-2.426000
-1.933600
-3.467000
-1.782800
-2.337000
-1.837200
-0.069100
0.829600
0.093500
1.465700
1.716800
2.512000
2.220100
0.965300
-0.378300
-0.401600
-0.103900
-1.751100
-1.743700
-2.468600
2-S0 xyz-coordinates
Au
1.429200 0.213000
Ag 4.003000 -0.490900
Cl
0.252900 1.384700
Cl
0.036000 4.380400
Cl
1.090100 6.592900
Cl
2.396400 5.794500
Cl
2.622600 2.807000
Cl
1.413600 -2.345300
Cl
1.590600 -5.353000
0.552200
0.379300
3.451800
4.247800
2.319400
-0.397500
-1.204600
2.665000
1.921800
Cl
Cl
Cl
C
C
C
C
C
C
C
C
C
C
C
C
S
S
S
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
Au
Ag
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
C
C
2.141900 -6.207800 -1.023600
2.453600 -4.040800 -3.242300
2.134400 -1.040000 -2.546400
1.354700 2.192000 1.116600
0.819400 2.595700 2.346000
0.724500 3.939200 2.733700
1.202000 4.936900 1.873300
1.783600 4.573300 0.651200
1.856500 3.217100 0.306300
1.744200 -1.777100 0.036000
1.649000 -2.790900 1.005000
1.745700 -4.154400 0.698200
1.982900 -4.545000 -0.627300
2.108700 -3.567000 -1.622600
1.974700 -2.215100 -1.279900
5.267100 0.303900 -1.820900
5.727200 -2.484800 0.314900
5.919400 0.787000 1.631000
5.989100 -1.308100 -2.253500
6.713800 -2.100800 -1.172600
6.796200 -1.908700 1.669300
7.254400 -0.454700 1.674000
6.405000 1.858100 0.239200
6.680400 1.212900 -1.113000
7.286900 2.442800 0.545700
7.550500 0.540900 -1.068900
6.198000 -2.130000 2.567600
7.833100 -0.286500 2.595700
7.631100 -1.587100 -0.848800
5.561000 2.562400 0.161000
6.944700 2.016700 -1.817700
7.939500 -0.253300 0.837600
7.031700 -3.059900 -1.609800
6.673900 -1.173200 -3.106100
5.117800 -1.866400 -2.633100
7.684100 -2.559400 1.714900
-1.426000 0.216000 -0.551400
-4.003600 -0.472700 -0.378600
-0.245400 1.382700 -3.451100
-0.018300 4.377300 -4.248300
-1.064900 6.594100 -2.320800
-2.373800 5.801300 0.396500
-2.610600 2.814900 1.204600
-1.422200 -2.343300 -2.663600
-1.618700 -5.349700 -1.920000
-2.176600 -6.200300 1.025400
-2.474900 -4.030900 3.243700
-2.136500 -1.032300 2.547200
-1.344500 2.194600 -1.116200
-0.807800 2.596000 -2.345800
C
C
C
C
C
C
C
C
C
C
S
S
S
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
-0.708400
-1.182400
-1.765200
-1.842900
-1.750100
-1.660700
-1.766400
-2.006600
-2.126400
-1.983700
-5.267600
-5.733600
-5.914100
-5.995400
-6.721400
-6.799000
-7.252800
-6.397900
-6.677000
-7.277600
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-2.529300
-2.734100
-1.874000
-0.651800
-0.306400
-0.034800
-1.003600
-0.696600
0.628900
1.624000
1.281100
1.821100
-0.319200
-1.632000
2.250500
1.167300
-1.674400
-1.678500
-0.238900
1.111900
-0.545500
1.065600
-2.572100
-2.600900
0.842900
-0.158700
1.817400
-0.843000
1.602700
3.102400
2.630400
-1.721900
2-T1 xyz-coordinates
Au -1.351200 0.188100
Ag -3.872900 -0.793000
Cl -0.695300 1.399300
Cl -0.736300 4.409200
Cl -1.547300 6.577600
Cl -2.380000 5.713800
Cl -2.344700 2.704400
Cl -1.753700 -2.213000
Cl -1.709600 -5.273300
Cl -1.729200 -6.342300
Cl -1.773200 -4.339900
Cl -1.781500 -1.275600
C
-1.424400 2.172600
C
-1.113900 2.594000
C
-1.143400 3.940500
C
-1.517600 4.917500
-0.229400
-0.028200
-3.249800
-4.056000
-1.961700
0.923500
1.722700
-2.493500
-1.949100
0.980800
3.375100
2.842600
-0.767800
-2.067200
-2.451700
-1.517300
C
C
C
C
C
C
C
C
Au
Ag
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
C
C
C
C
C
C
C
C
C
C
C
C
S
S
S
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
-1.879500
-1.833900
-1.722300
-1.701600
-1.701800
-1.710300
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1.596600
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2.612500
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0.546900
-2.415700
-0.220000
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0.190600
-0.858500
-0.634700
0.686200
1.761800
1.505400
0.229400
0.028300
3.250000
4.056800
1.962700
-0.922900
-1.722600
2.493800
1.949900
-0.979900
-3.374500
-2.842600
0.768000
2.067600
2.452400
1.518000
0.220600
-0.123300
-0.190400
0.858800
0.635300
-0.685500
-1.761300
-1.505100
1.950000
-0.436700
-1.504000
2.098300
0.827500
-1.937500
-1.902500
-0.160500
1.070300
-0.583000
0.826300
-2.700100
-2.898900
0.357600
0.122000
1.778700
-1.194300
1.104800
H
H
H
S
S
S
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
-7.394900
-6.044800
-7.612600
5.359300
6.083200
5.123600
6.598500
7.244400
6.633600
6.703100
5.576000
6.273900
6.194200
7.277500
5.915400
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