1 Highly stable 7-N,N-Dibutylamino-2-azaphenanthrene and 8-N,N- dibutylamino-2-azachrysene as a new class of second order NLO- active chromophores Valentina Calabrese, Silvio Quici, Ester Rossi, Elena Cariati, Claudia Dragonetti, Dominique Roberto, Elisa Tordin, Filippo De Angelis and Simona Fantacci ESI Synthesis of the various compounds: Synthetic scheme a Cl NBu 2 PPh3 + Cl - NBu2 NBu2 N NBu2 N 1 2 3 NBu2 N Ir(CO)2Cl 4 (L 3 ) 2 NBu2 N NBu2 N 5 (IrL 3 ) 7(L 4 ) NBu 2 N NBu2 N I - Ir(CO)2Cl 6 (a) (b) (c) (d) (e) (f) (g) (h) 8 (IrL 4 ) 9 (L 4 MeI) NMe2 N Br N NMe 2 B(OH)2 + HCl 10 (L 1 ) OH NB u2 (i) 6 (l) a Reagents and conditions: (a) PPh 3 , CCl 4 , THF, 48 h, 95%; (b) PPh 3 , heptane, reflux, 24 h, 82%; (c) 3-pyridinecarboxaldehyde, t BuOK, dry MeOH, N 2 , reflux, overnight, 82%; (d) 2-Me-THF, hν, 1.5 h, -15 °C, 46%; (e) [Ir-(COT) 2 Cl] 2 , dry CH 3 CN, CO, 1 h, quantitative; (f) isoquinoline-5- carbaldehyde, t BuOK, dry MeOH, N 2 , reflux, overnight, 82%; (g) THF, hν, 8 h, 17 °C, 33.5%; (h) [Ir-(COT) 2 Cl] 2 , dry CH 3 CN, CO, 1 h, quantitative; (i) THF, MeI, RT, overnight, 85% (l) acqueous Na 2 CO 3 tetrakis(triphenylphosphine)palladium(0), THF, 80 °C, 18 h, 79%. Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2010
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Highly stable 7-N,N-Dibutylamino-2-azaphenanthrene and 8-N,N-dibutylamino-2-azachrysene as a new class of second order NLO-active chromophores Valentina Calabrese, Silvio Quici, Ester Rossi, Elena Cariati, Claudia Dragonetti, Dominique Roberto, Elisa Tordin, Filippo De Angelis and Simona Fantacci
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010
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Compound 7
283 nm
420 nm
272 nm
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
230 280 330 380 430 480 530 580
nm
Abs
orba
nce
Compound 8
473 nm
364 nm
315 nm
285 nm272 nm
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
240 290 340 390 440 490 540 590
nm
Abs
orba
nce
Compound 9
251 nm
506 nm
417nm
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
240 290 340 390 440 490 540 590
nm
Abs
orba
nce
NMe2
N
NBu2
N
Ir(CO)2Cl
NBu2
N I-
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L3 optimized molecular structure in CHCl3 solution: N 6.334882 -0.498960 -0.117160 C 5.602164 -1.562032 -0.531317 C 5.653288 0.567533 0.280809 C 4.244304 0.662547 0.299568 C 3.482534 -0.459635 -0.137363 C 4.220759 -1.590193 -0.559264 C 3.578025 1.852577 0.744500 C 2.219412 1.924974 0.757406 C 1.404623 0.816994 0.328244 C 2.037458 -0.379412 -0.124332 C 0.001242 0.918839 0.348780 C -0.832005 -0.135390 -0.061087 C -0.182528 -1.326759 -0.510411 C 1.191148 -1.432920 -0.538782 H 6.241128 1.425493 0.615108 H 6.171752 -2.432646 -0.855985 H 3.721492 -2.489535 -0.908360 H 4.183080 2.696596 1.072384 H 1.719497 2.830749 1.097201 H -0.423364 1.858138 0.684077 H 1.620300 -2.368799 -0.887098 H -0.767592 -2.183097 -0.824863 N -2.209072 -0.040894 -0.030800 C -2.884171 1.121671 0.543068 C -3.074187 -1.081997 -0.584833 C -3.113041 2.274082 -0.449288 H -3.851673 0.781275 0.932119 H -2.319896 1.475973 1.413554 C -3.440336 -2.195323 0.410396 H -3.991723 -0.592728 -0.933915 H -2.608248 -1.509536 -1.479844 C -4.385519 -3.238999 -0.197554 H -2.523082 -2.684499 0.765116 H -3.909409 -1.742050 1.295279 C -4.769829 -4.347285 0.788270 H -5.295849 -2.738368 -0.557962 H -3.912656 -3.686164 -1.083968 H -5.443563 -5.076789 0.324425 H -3.883501 -4.888640 1.141314 H -5.278580 -3.935363 1.668536 C -3.834509 3.466143 0.192625 H -2.148210 2.599217 -0.860667 H -3.701024 1.900921 -1.299793 C -4.086706 4.614100 -0.790465 H -4.792407 3.127446 0.613265 H -3.241929 3.834982 1.042223 H -4.602059 5.450102 -0.303897 H -3.144730 4.996397 -1.202630 H -4.706808 4.284102 -1.633024
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L4 optimized molecular structure in CHCl3 solution: C 5.236846 -0.924111 -0.275644 C 4.385856 -2.004439 -0.651952 C 4.664539 0.309008 0.149141 C 3.224623 0.447109 0.192113 C 2.402958 -0.646502 -0.190788 C 3.028334 -1.867546 -0.610360 C 2.601581 1.664811 0.612751 C 1.244198 1.797304 0.655118 C 0.377723 0.722278 0.278227 C 0.963102 -0.507658 -0.150943 C -1.022403 0.882374 0.321388 C -1.902256 -0.144954 -0.046050 C -1.304881 -1.373578 -0.470773 C 0.061066 -1.537400 -0.519404 C 5.580720 1.329963 0.505156 H 4.836819 -2.941807 -0.973877 H 2.412191 -2.711237 -0.904040 H 3.217948 2.508563 0.907791 H 0.798427 2.735750 0.981223 H -1.400263 1.847834 0.638096 H 0.435552 -2.501998 -0.848814 H -1.928286 -2.214888 -0.750587 N -3.275239 0.001462 0.000508 C -3.895255 1.206955 0.545964 C -4.185963 -1.009936 -0.534255 C -4.078205 2.342233 -0.475561 H -4.874636 0.920675 0.948719 H -3.309973 1.558395 1.403773 C -4.599135 -2.090389 0.478715 H -5.082368 -0.487649 -0.890641 H -3.741157 -1.472551 -1.422609 C -5.586018 -3.103373 -0.114927 H -3.703540 -2.611698 0.843042 H -5.050056 -1.603836 1.355336 C -6.014733 -4.181918 0.885377 H -6.475175 -2.571158 -0.482827 H -5.131545 -3.581336 -0.994905 H -6.717206 -4.889891 0.430857 H -5.150841 -4.753712 1.246008 H -6.506555 -3.738438 1.759899 C -4.742547 3.582107 0.136397 H -3.101784 2.613090 -0.898732 H -4.686071 1.973295 -1.313873 C -4.941985 4.715662 -0.875084 H -5.714795 3.299599 0.565615 H -4.132287 3.944219 0.976371 H -5.416681 5.586948 -0.409450 H -3.983647 5.042665 -1.297007 H -5.578235 4.394282 -1.708892 C 6.938736 1.096310 0.428095
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N 7.490850 -0.077117 0.023652 C 6.647301 -1.040175 -0.311717 H 5.239419 2.304266 0.841064 H 7.643587 1.880981 0.701514 H 7.086672 -1.985575 -0.638088
Figure S1:Optimized molecular structure of L3 and L4.
Figure S2:Optimized molecular structure of IrL3 and IrL4 complexes with selected bond distances
and bond and dihedral angles.
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Figure S3: Schematic representation of frontier molecular orbitals of L3 and L4
Figure S4. Isodensity plots of the electron density difference between S1-S5 excited states and the
ground state of L3 and L4 ligands. A red (blue) color indicates a decrease (increase) of the electron
density upon excitation. The excitation wavelengths, oscillator strengths are also reported.
Full reference 14:
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Gaussian 03, Revision C.02, M. J. Frisch G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
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Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010