Highly efficient thermally activated fluorescence of a new

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Highly efficient thermally activated fluorescence of a new rigid Cu I complex Cu dmp Cryovac Konti Cryostat IT in which the helium gas ow gas

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Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. Quantum chemical computations were performed using the Gaussian09 computer programs suite3. Contour plots of the resulting molecular orbitals were drawn using the GaussView program. 2 Synthesis of Cu dmp phanephos PF6, 37 mg of Cu CH3CN 4 PF6 0 1 mmol and 58 mg of Rp 4 12 bis diphenylphosphino. 2 2 paracyclophane Rp phanephos 0 1 mmol were dissolved in 25 ml of dry acetonitrile saturated. with argon The mixture was stirred at room temperature for 2 hours Subsequently 21 mg of. 2 9 dimethyl 1 10 phenanthroline dmp 0 1 mmol were added and the mixture was stirred for another. 2 hours The solvent was evaporated and the inorganic salts were removed by passing the reaction. mixture through a short column filled with neutral aluminum oxide using dichloromethane as eluent. Along with the target complex Cu dmp phanephos PF6 a small amount of deeply red colored. homoleptic complex Cu dmp 2 PF6 formed as a byproduct Our attempts to separate these complexes. by means of column chromatography turned out to be unsatisfactory Thus Cu dmp phanephos PF6. was purified by several consecutive crystallizations from dichloromethane ethyl acetate solutions 1 10. volume ratio at 30 C The resulting material gave correct results of elemental analyses Found C. 64 87 H 4 67 N 2 68 required for CuC58H54N2O2P3F6 C 64 41 H 5 03 and N 2 59 The mass. spectra electro spray displayed a characteristic set of signals at m z 847 4 M The crystallizations. were performed until maximal values of the emission quantum yield PL 80 and decay time. 14 s were determined for solid samples Table 1 i e until emission quenching effects due to residual. impurities most of all due to the Cu dmp 2 PF6 byproduct were minimized Yield 30. H NMR 600 MHz CD2Cl2 8 62 d J 8 4 Hz 2H dmp 8 17 s 2H dmp 7 74 d J 8 4 Hz. 2H dmp 7 55 t J 9 0 Hz 2H phanephos pCp 7 39 7 36 m 4H phanephos Ph 7 29 t J 7 2. Hz 2H phanephos Ph 7 16 t J 7 8 Hz 4H phanephos Ph 7 09 t J 7 2 Hz 2H phanephos. Ph 6 93 d J 7 8 Hz 2H phanephos pCp 6 85 dd J 8 4 Hz 1 2 Hz 2H phanephos pCp 6 81. t J 7 2 Hz 4H phanephos Ph 6 48 6 47 m 4H phanephos Ph 3 13 3 09 m 2H phanephos. pCp 2 89 2 85 m 2H phanephos pCp 2 76 2 72 m 2H phanephos pCp 2 30 2 24 m 2H. phanephos pCp 1 56 s 6H dmp pCp paracyclophane Ph phenyl Fig S1. P NMR 121 MHz CD2Cl2 2 19 s phanephos 143 90 hept PF6. The same procedure was applied to the second enantiomer of the phanephos ligand Sp 4 12. bis diphenylphosphino 2 2 paracyclophane Sp phanephos affording Cu dmp Sp phanephos PF6. Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. Figure S1 1H NMR spectrum for Cu dmp phanephos PF6 recorded in CD2Cl2 c 12 M Signals. marked with an asterisk are due to protons of CDHCl2 H2O and ethyl acetate. Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. 3 Crystal structures, Crystals suitable for x ray analysis were obtained from dichloromethane ethyl acetate 1 10 volume. ratio solutions at 30 C Cu dmp phanephos PF6 crystallizes in the non centrosymmetric. orthorhombic crystal system In addition to the Cu dmp phanephos and PF6 ions the asymmetric. unit contains also one ethyl acetate solvent molecule The molecular structures of the two enantiomeric. Cu dmp Rp phanephos and Cu dmp Sp phanephos ions and atom numbering schemes are. displayed in Fig S2 Relevant bond lengths and angles are summarized in Table S2. Figure S2 Molecular views thermal ellipsoids at the 50 probability level on the Cu dmp phanephos. ions A phanephos enantiomer Rp B phanephos enantiomer Sp The PF6 ions and solvent molecules are. omitted for clarity, Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. Table S1 Crystal data data collection and structure refinement details. Cu dmp Rp phanephos PF6 Cu dmp Sp phanephos PF6,CH3CO2C2H5 CH3CO2C2H5. crystal shape prism prism,crystal color faint yellow faint yellow.
empirical formula C58 H54 Cu F6 N2 O2 P3 C58 H54 Cu F6 N2 O2 P3. formula weight 1081 49 1081 49, crystal size mm 0 6690 0 5778 0 3652 0 3145 0 1752 0 1534. crystal system orthorhombic orthorhombic,space group P 21 21 21 P 21 21 21. a 16 4869 2 16 5204 4,b 17 65670 17 17 5982 3,c 18 69160 19 18 7370 3. cell volume 3 5441 21 10 5447 40 18,density g cm 1 1 320 1 319. absorption 1 934 1 931,coefficient mm 1,F 000 2240 2240.
T K 293 297,1 54184 1 54184,range 3 44 63 39 3 4426 63 4135. reflections collected 19860 22288,unique reflections 8583 8045. observed reflections 8263 7179,absorption correction analytical analytical. GOF 1 032 1 026,final R1 I 2 I 0 0399 0 0457,wR2 0 1089 0 1190. Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. Table S2 Selected bond lengths and angles for Cu dmp phanephos Atom numbering is given in. Cu dmp Rp phanephos Cu dmp Sp phanephos,Cu1 N1 2 108 3 Cu1 N2 2 105 3.
Cu1 N2 2 115 2 Cu1 N1 2 116 3,Cu1 P1 2 3142 8 Cu1 P1 2 3147 10. Cu1 P2 2 3049 8 Cu1 P2 2 3046 11,P1 C39 1 836 3 P1 C39 1 828 4. P2 C51 1 825 3 P2 C47 1 827 4,P1 P2 3 912 P1 P2 3 908. N1 Cu1 N2 80 20 10 N1 Cu1 N2 80 28 13,P1 Cu1 P2 115 74 3 P1 Cu1 P2 115 58 4. P1 Cu1 N1 117 04 7 P1 Cu1 N1 117 99 9,P1 Cu1 N2 109 58 7 P1 Cu1 N2 112 01 10.
P2 Cu1 N1 111 93 8 P2 Cu1 N2 116 86 10,P2 Cu1 N2 117 61 7 P2 Cu1 N1 109 47 9. P1 P2 N2 N1 71 39 P1 P2 N1 N2 71 85, Cu dmp phanephos exhibits a four coordinated metal center with a distorted tetrahedral. geometry The P Cu P and N Cu N angles of about 116 and 80 respectively strongly deviate from. the value of 109 of an ideal tetrahedron This reflects distinctly different steric requirements of the. phanephos and dmp ligands In particular the P Cu P angle formed for the phanephos ligand matches. with the largest value reported for the wide bite angle pop ligand that coordinates with a P Cu P angle. in the range between 108 and 116 4 The rigid paracyclophane group and the two diphenylphosphine. functions separated by a P1 P2 distance of about 3 9 form a firm semi cage occupied by the metal ion. and the dmp ligand Moreover the overall bulkiness of the phenaphos ligand and the methyl groups of. dmp around the metal center seem to provide a good shielding of the potentially photo reactive metal. centre from direct contact with solvent molecules, Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. 4 Electronic transitions TD DFT calculations, Time dependent density functional calculations were performed for the molecular geometry of. Cu dmp Rp phanephos resulting from the x ray diffraction measurements Five lowest energy. singlet and triplet transitions were calculated using the B3LYP 5 functional and the SVP6 atomic orbital. basis set for all atoms The results are summarized in Table S3 and Figure S3 In particular the lowest. excited states S1 and T1 are predicted to have a distinct charge transfer character where electron density. is shifted from the metal center and the aromatic system of the phanephos ligand to the dmp ligand This. result substantiates the MLCT nature of the S1 and T1 states The calculated energy separation between. the two states E S1 T1 amounts to 1540 cm 1 However the TD DFT computation has been carried. out for the ground state conformation regardless of any geometry reorganization taking place upon. excitation Thus taken this approximation and also in view of the known problems regarding the. prediction of transition energies of charge transfer excited states by TD DFT 7 the calculated singlet. triplet splitting being about 50 larger than the E S1 T1 value determined experimentally from the. decay time analysis is regarded to be in a fair agreement. Figure S3 Contour plots of the natural transition orbitals8 obtained for the lowest excited singlet state. S1 of Cu dmp phanephos on the B3LYP SVP TD DFT theory level. Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. Table S3 Calculated energy levels oscillator strengths f and orbital analyses for the five lowest. singlet and triplet transitions in Cu dmp phanephos. transition energy cm 1 f assignement character,S0 T1 21130 0 HOMO LUMO 92 d dmp.
S0 S1 22670 0 0621 HOMO LUMO 78 d dmp,S0 T2 23550 0 HOMO 3 LUMO 1 70 d dmp. HOMO LUMO 1 14,S0 T3 23570 0 HOMO LUMO 1 46 d dmp,HOMO 3 LUMO 22. S0 T4 24300 0 HOMO 1 LUMO 6 22 d phan phan,HOMO LUMO 2 18. HOMO 4 LUMO 2 14,HOMO 1 LUMO 4 9,HOMO 5 LUMO 11 6,S0 T5 24390 0 HOMO 2 LUMO 50 d phan dmp. HOMO 1 LUMO 42,S0 S2 24750 0 0024 HOMO 3 LUMO 87 d phan dmp.
HOMO 1 LUMO 5,S0 S3 25040 0 0036 HOMO 1 LUMO 48 d phan dmp. HOMO 2 LUMO 42,HOMO 3 LUMO 6,S0 S4 25240 0 0088 HOMO LUMO 2 95 d dmp. S0 S5 25490 0 0004 HOMO 2 LUMO 52 d phan dmp,HOMO 1 LUMO 46. Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. Figure S4 Molecular orbitals active space important for the low energy electronic transitions of. Cu dmp phanephos listed in Table S3, 5 Estimation of the radiative decay rate of the S1 S0 transition. For a two state model i e the ground state and an excited state spontaneous emission probability is. directly proportional to the corresponding absorption strength molar extinction and to the third power. of the energy separation between these states The relationship between the radiative decay rate of the. spontaneous S1 S0 emission kr S1 and the S0 S1 absorption strength can be expressed as 9. k r S1 8 ln10 c n 2 N A fl d abs S1, where c is the speed of light in vacuum NA is the Avogadro constant and n is the refractive index of the.
medium fl represents the reciprocal of the mean value of the third power of the fluorescence. energy fl cm 1 weighted with the emission intensity at each fl value of the fluorescence spectrum. and the integral abs, d abs represents the absorption strength of the S0 S1 absorption band abs. is the molar absorption coefficient at a given energy abs If fl is approxiamted by the third power. of the emission maximum max eq S1 can be expressed as. Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. k r S1 const n 2 max,with const 2 88 10 12 s 1 mol cm. From an integration of the lowest absorption band of Cu dmp phanephos PF6 dissolved in. dichloromethane n 1 42 measured at ambient temperature an approximate value of abs. 3 7 105 cm2 mol 1 is be obtained Fig S5 For max a value of 17500 cm 1 CH2Cl2 300 K is taken. Thus a radiative decay rate of the spontaneous S1 S0 fluorescence of kr S1 1 2 107 s 1. corresponding to a radiative decay time for the S1 S0 transition of r 80 ns is obtained. Figure S5 Ambient temperature absorption spectrum of Cu dmp phanephos PF6 in CH2Cl2. Compare Fig 1 The red shaded area marks approximately the S0 S1 absorption band The. calculated 0 0 lines energy TD DFT level of the S0 S1 transition is also displayed The TD DFT. calculations reveal a series of additional charge transfer transitions at energies close to that of the S0. S1 transition However according to their very small oscillator strengths f Table S3 they were. neglected for the approximate analysis of the lowest energy 1MLCT absorption strength. References, S1 A Altomare G Cascarano C Giacovazzo A Guagliardi J Appl Crystallogr 1993 26 343. S2 G M Sheldrick SHELXL 97 Program for crystal structure refinement University of. G ttingen Germany 1997, Electronic Supplementary Material ESI for Dalton Transactions. This journal is The Royal Society of Chemistry 2013. S3 Gaussian09W Version 8 0 M J Frisch G W Trucks H B Schlegel G E Scuseria M A. Robb J R Cheeseman G Scalmani V Barone B Mennucci G A Petersson H Nakatsuji M. Caricato X Li H P Hratchian A F Izmaylov J Bloino G Zheng J L Sonnenberg M Hada. M Ehara K Toyota R Fukuda J Hasegawa M Ishida T Nakajima Y Honda O Kitao H. Nakai T Vreven J A Montgomery Jr J E Peralta F Ogliaro M Bearpark J J Heyd E. Brothers K N Kudin V N Staroverov R Kobayashi J Normand K Raghavachari A. Rendell J C Burant S S Iyengar J Tomasi M Cossi N Rega J M Millam M Klene J E. Knox J B Cross V Bakken C Adamo J Jaramillo R Gomperts R E Stratmann O Yazyev. A J Austin R Cammi C Pomelli J W Ochterski R L Martin K Morokuma V G. Zakrzewski G A Voth P Salvador J J Dannenberg S Dapprich A D Daniels Farkas J. B Foresman J V Ortiz J Cioslowski and D J Fox Gaussian Inc Wallingford CT 2009. S4 a M G Crestani G F Manbeck W W Brennessel T M McCormick R Eisenberg Inorg. Chem 2011 50 7172 b R Venkateswaran M S Balakrishna S M Mobin H M. Tuononen Inorg Chem 2007 46 6535 c D G Cuttel S M Kuang P E Fanwick D R. McMillin R A Walton J Am Chem Soc 2001 124 6 d S M Kuang D G Cuttel D R. McMillin P E Fanwick R A Walton Inorg Chem 2002 41 3313 e J Xu D Yun B Lin. Synth Met 2011 161 1276 f P Aslanidis P J Cox A C Tsipis Dalton Trans 2010 39. 10238 g C W Hsu C C Lin M W Chung Y Chi G H Lee P T Chou C H Chang P. Y Chen J Am Chem Soc 2011 133 12085 h R Czerwieniec J Yu H Yersin Inorg. Chem 2011 50 8293 i L Qin Q Zhang W Sun J Wang C Lu Y Cheng L Wang. Dalton Trans 2009 9388 j Q Zhang J Ding Y Cheng L Wang Z Xie X Jing F Wang. Adv Funct Mater 2007 17 2983 k C Femoni S Muzzioli A Palazzi S Stagni S. Zacchini F Monti G Accorsi M Bolognesi N Armaroli M Massi G Valenti M. Marcaccio Dalton Trans 2013 42 997, S5 a A D Becke J Chem Phys 1993 98 5648 b P J Stephens F J Devlin C F.
Chabalowski M J Frisch J Phys Chem 1994 98 11623, S6 A Schaefer H Horn R Ahlrichs J Chem Phys 1992 97 2571. S7 a A Dreuw M Head Gordon J Am Chem Soc 2004 126 4007 b P Wiggins J A G. Williams D J Tozer J Chem Phys 2009 131 091101 c Z L Cai M J Crossley J R. Reimers R Kobayashi R D Amos J Phys Chem B 2006 110 15624. S8 R L Martin J Chem Phys 2003 118 4775,S9 S J Strickler R A Berg J Chem Phys 1962 37 814.

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