Supporting Information for Syntheses and Characterizations of Molecular Hexagons and Rhomboids and Subsequent Encapsulation of Keggin-Type Polyoxometalates by Molecular Hexagons Kazuhiro Uehara, Takamichi Oishi, Takayuki Hirose, and Noritaka Mizuno* Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan Contents Details of X-ray Crystallography Details of DFT calculations Figure S1. IR spectrum of [(en)pd(l)] 3 (OTf) 6 1t OTf (KBr, cm 1 ) Figure S2. IR spectrum of [(en*)pd(l)] 2 (PF 6 ) 4 2d PF 6 (KBr, cm 1 ) Figure S3. IR spectrum of {[(dppe)pd(l)](otf) 2 } 3 OTf (KBr, cm 1 ) Figure S4. IR spectrum of [(en*)pd(l)] 3 [ α-pw 12 O 40 ](NO 3 ) 3 S3 S4 S14 S15 S16 S17 Figure S5. CSI-MS spectrum of {[(dppe)pd(l)](otf) 2 } 3 OTf (263 K, MeCN) S18 Figure S6. NMR spectra of [(en)pd(l)] 3 (OTf) 6 1t OTf in DMSO-d 6, (a) 1 H line (500 MHz), 13 C{H} line (124.50 MHz), and (c) 19 F line (465.89 MHz) S19 Figure S7. NMR spectra of [(en*)pd(l)] 2 (PF 6 ) 4 2d PF 6 in DMSO-d 6, (a) 1 H line (500 MHz), (b) 13 C{H} line (124.50 MHz), (c) 31 P{H} line (200.43 MHz), and (d) 19 F line (465.89 MHz). S21 Figure S8. NMR spectra of {[(dppe)pd(l)](otf) 2 } 3 OTf in DMSO-d 6, (a) 1 H line (500 MHz), (b) 13 C{H} line (124.50 MHz), (c) 31 P{H} line (200.43 MHz) and (d) 19 F line (465.89 MHz) Figure S9. 1 H DOSY spectrum of [(en)pd(l)] n (OTf) 2n 1t/1d OTf (n = 2, 3) (DMSO-d 6, 303 S23 S1
K) S25 Figure S10. Curve fitting analysis of 1 H DOSY NMR for [(en)pd(l)] 3 (OTf) 6 1t OTf Figure S11. Curve fitting analysis of 1 H DOSY NMR for [(en)pd(l)] 2 (OTf) 4 1d OTf S26 S27 Figure S12. Curve fitting analysis of 19 F DOSY NMR for [(en)pd(l)] n (OTf) 2n 1t/1d OTf (n = 2, 3) S28 Figure S13. 1 H DOSY spectrum of [(en*)pd(l)] n (PF 6 ) 2n 2t/2d PF 6 (n = 2, 3) (DMSO-d 6, 303 K) S29 Figure S14. Curve fitting analysis of 1 H DOSY NMR for [(en*)pd(l)] 2 (PF 6 ) 4 2t PF 6 S30 Figure S15. Curve fitting analysis of 1 H DOSY NMR for [(en*)pd(l)] 2 (PF 6 ) 4 2d PF 6. S31 Figure S16. Curve fitting analysis of 31 P DOSY NMR for [(en*)pd(l)] n (PF 6 ) 2n 2t/2d PF 6 S32 Figure S17. Curve fitting analysis of 1 H DOSY NMR for {[(dppe)pd(l)] 2 (OTf) 2 } 3 OTf S33 Figure S18. Curve fitting analysis of 19 F DOSY NMR for {[(dppe)pd(l)] 2 (OTf) 2 } 3 OTf S34 Figure S19. 1 H DOSY spectrum of [(en*)pd(l)] n (PF 6 ) 2n 2t/2d PF 6 (n = 2, 3) in the presence of H 3 [α-pw 12 O 40 ] (DMSO-d 6, 303 K) S35 Figure S20. Curve fitting analysis of 1 H DOSY NMR for {[(en*)pd(l)] 3 [[ α-pw 12 O 40 ]](PF 6 ) 3 2t [α-pw 12 O 40 ] 3 S36 Figure S21. Curve fitting analysis of 1 H DOSY NMR for {[(en*)pd(l)] 2 [α-pw 12 O 40 ]}(PF 6 ) 2d [α-pw 12 O 40 ] 3 S37 Figure S22. Curve fitting analysis of 31 P DOSY NMR for {[(en*)pd(l)] 3 [ α-pw 12 O 40 ]}(PF 6 ) 3 2t [α-pw 12 O 40 ] 3 S38 Figure S23. Curve fitting analysis of 31 P DOSY NMR for H 3 [α-pw 12 O 40 ] S39 References S40 S2
Details of X-ray crystallography. Diffraction measurements for 1t OTf, 2d PF 6, and 3 W 6 O 19 were made on Rigaku MicroMax-007 with Mo Kα radiation (λ = 0.71069 Å). The data collections were carried out at 153 K. Indexing was performed from 12 oscillation images, which were exposed for 5 s. The crystal-to-detector distance was 45 mm. Readout was performed with the pixel size of 72.4 72.4 mm. A sweep of data was done using ω scans from 110 to 70 at κ = 45 and φ = 0, 90. A total of 720 images for each compound were collected. Neutral scattering factors were obtained from the standard source. 1 Data were corrected for Lorentz and polarization effects. Empirical absorption corrections were made with HKL 2000 for Linux. 2 Molecular structures were solved by SHELX-97 3 linked to Win-GX for Windows 4. Total of six and four anions for 1t OTf and 2d PF 6 were confirmed, but highly disordered. Therefore, the SQUEEZE program of PLATON was used to remove the electron density on the Fourier map derived from the disordered solvents of crystallization. 5 Cationic parts for 1t OTf, 2d PF 6, and 3 W 6 O 19 were refined anisotropically. Tungsten atoms of hexatungstate in 3 W 6 O 19 were refined anisotropically, whereas oxygen atoms of hexatungstate in 3 W 6 O 19 were refined isotropically. Hydrogen atoms for 1t OTf, 2d PF 6, and 3 W 6 O 19 were refined as a riding model. As for 3 W 6 O 19, parts of phenyl groups of dppe ligand in 3 W 6 O 19 were disordered. The disordered atom sets were (C21A C26A, C21B C26B) and (C61A C66A, C61B C66B), and the respective occupancies were 0.51, 0.49) and (0.39, 0.61), respectively. Hydrogen atoms for these parts were not refined. Crystallographic data for compounds 1t OTf (CCDC-942775), 2d PF 6 (CCDC-942776), and 3 W 6 O 19 (CCDC-942777) are available free of charge from the Cambridge Crystallographic Data Center. S3
Details of DFT calculations. 6-14 DFT calculations were performed with Gaussian 09 software. Cationic parts of 1t OTf and 2h PF 6 were optimized using 6-31G* (C, H, N) /LanL2DZ (Pd) (6D, 7F) with B3LYP level of theory, taking into account the solvation in DMSO with the conductor-like polarizable continuum model (IEFPCM) with the parameter sets of United Atom Topological Model (UAKS). The corresponding single-point energy calculation was carried out using 6-311++G** (C, H, N) / LanL2DZ (Pd) basis sets with B3LYP level of theory, taking into account the solvation in DMSO with the conductor-like polarizable continuum model (IEFPCM) with the parameter sets of United Atom Topological Model (UAKS). Cartesian coordinates of [(en)pd(l)] 4+ 2 in DMSO. C 1 symmetry -2391.7540444 Hartree -2392.32393227 hartree (single-point) Pd 8.108711-0.034334-0.907367 C -5.627638-2.833284 1.186594 Pd -8.110059 0.035174-0.902102 H -5.657840-3.279290 2.178600 N -9.535695-1.368234-1.453759 C -6.655715-1.997910 0.775764 N 9.631955-1.371888-1.357472 H -7.498444-1.779583 1.428936 N 9.534821 1.367674-1.461197 C -3.417598-3.835687 0.733571 N -6.661135-1.402374-0.435443 C -2.421182-4.429495 1.099707 C -5.646086-1.651179-1.288593 C -1.213148-5.052823 1.533387 H -5.695641-1.163652-2.260372 C 0.016810-4.547308 1.079978 C -4.577634-2.467538-0.951775 H 0.034848-3.711217 0.383863 H -3.772411-2.626205-1.666102 C 1.223963-5.092963 1.548278 C -4.540073-3.065462 0.322818 C 1.193616-6.173724 2.452569 H 2.128925-6.597314 2.814711 C 1.212949 5.061348 1.515253 S4
C -0.029248-6.689599 2.880275 C -0.017635 4.554250 1.065346 H -0.047229-7.526683 3.576697 H -0.036666 3.715453 0.372519 C -1.229122-6.134054 2.437793 C -1.224123 5.101905 1.533031 H -2.182183-6.526674 2.788357 C -1.192509 6.186185 2.433033 C 2.455503-4.507220 1.127904 H -2.127305 6.611330 2.794675 C 3.468826-3.937953 0.769363 C 0.030964 6.703571 2.857163 N 6.716455-1.518238-0.413271 H 0.049932 7.543394 3.550255 C 5.723752-1.809973-1.279312 C 1.230205 6.146118 2.415375 H 5.786765-1.352938-2.265101 H 2.183757 6.539983 2.763194 C 4.658728-2.628452-0.938152 C 2.420418 4.436184 1.082577 H 3.869926-2.819675-1.662747 C 3.416420 3.840945 0.717654 C 4.600189-3.182133 0.355453 N 6.659845 1.404200-0.444438 C 5.669338-2.912958 1.231275 C 5.646454 1.653137-1.299484 H 5.684559-3.326558 2.237580 H 5.697307 1.164979-2.270882 C 6.695868-2.077945 0.814497 C 4.578025 2.470534-0.965002 H 7.522350-1.828218 1.477112 H 3.774133 2.629324-1.680801 C 10.698897-0.660981-2.124861 C 4.538809 3.069397 0.309084 H 10.355872-0.575522-3.168556 C 5.624710 2.836944 1.174886 H 11.638539-1.238591-2.103438 H 5.653554 3.283614 2.166633 C 10.876934 0.712758-1.506549 C 6.652825 2.000501 0.766391 H 11.241735 0.629201-0.470103 H 7.494276 1.781941 1.421126 H 11.586037 1.327430-2.086580 N -9.633051 1.371605-1.356159 N -6.718267 1.520404-0.411371 C -10.877770-0.713432-1.501921 C -5.729049 1.814007-1.280749 H -11.586288-1.329397-2.081293 H -5.794806 1.357262-2.266500 H -11.243603-0.627577-0.466027 C -4.664022 2.633861-0.942887 C -2.456267 4.514713 1.116386 H -3.878002 2.826551-1.670113 C -3.470066 3.944242 0.761137 C -4.601803 3.187005 0.350763 C -10.699165 0.658957-2.123080 C -5.667513 2.915893 1.230167 H -11.638864 1.236559-2.103872 H -5.679835 3.329023 2.236706 H -10.355081 0.571262-3.166239 C -6.694270 2.079566 0.816591 H -9.273573-1.722009-2.397851 H -7.518057 1.828276 1.481966 H -9.288655 2.199882-1.881857 H 9.273553 1.719124-2.406397 H 9.287906-2.201144-1.881849 H 10.012400-1.726206-0.454693 H -10.014365 1.727631-0.454418 S5
H 9.545183 2.192793-0.828380 H -9.546665-2.191796-0.818930 Cartesian coordinates of [(en*)pd(l)] 4+ 2 in DMSO. C 1 symmetry -2706.16053163 hartree -2706.79787463 hartree (single-point) Pd -8.281966-0.001251-0.754265 H 0.001006 3.507347 0.534253 Pd 8.279908 0.002936-0.758799 C -1.208448 4.811655 1.765983 N 9.772964 1.396125-1.344905 C -1.194705 5.855123 2.713784 N -9.762655 1.451794-1.214716 H -2.136412 6.240241 3.101400 N -9.745425-1.415941-1.376049 C 0.019171 6.383649 3.150706 N 6.836099 1.457762-0.290556 H 0.024116 7.192083 3.880396 C 5.850887 1.728893-1.172332 C 1.226936 5.875623 2.674566 H 5.957618 1.303541-2.168712 H 2.174091 6.276447 3.031771 C 4.743921 2.492975-0.836357 C -2.435473 4.222337 1.337259 H 3.967008 2.672769-1.576650 C -3.457203 3.668646 0.978527 C 4.630624 3.007820 0.469533 N -6.817781 1.407734-0.210908 C 5.685293 2.751837 1.366948 6-5.868885 1.753193-1.106938 H 5.656850 3.133820 2.385406 H -6.005227 1.392932-2.125037 C 6.755457 1.972900 0.954291 C -4.764295 2.515338-0.761101 H 7.571955 1.736290 1.634192 H -4.017560 2.757135-1.514665 C 3.470097 3.718105 0.882219 C -4.615458 2.952219 0.569441 C 2.450007 4.259667 1.263779 C -5.630914 2.616678 1.485171 C 1.227626 4.831797 1.726902 H -5.573911 2.935338 2.524026 C 0.006010 4.314614 1.263866 C -6.700538 1.842122 1.061122 H -7.487221 1.544940 1.752499 C -1.224305-4.823959 1.742218 C -9.235625 2.617638-1.973545 C -0.001690-4.308384 1.280321 H -8.718931 2.263169-2.869982 H 0.004965-3.500967 0.550899 S6
H -8.542017 3.179420-1.343155 C 1.211766-4.807198 1.783028 H -10.072512 3.268560-2.264737 C 1.196057-5.850860 2.730559 C -10.384723 1.936918 0.049343 H 2.136969-6.237410 3.118690 H -9.624192 2.445781 0.648083 C -0.018914-6.377749 3.166527 H -10.790307 1.096375 0.617522 H -0.025498-7.186322 3.896047 H -11.193149 2.642671-0.190261 C -1.225710-5.868045 2.689620 C -10.767290 0.728151-2.064816 H -2.173638-6.267743 3.046047 H -10.347906 0.665244-3.081434 C -2.444630-4.249251 1.277416 H -11.701349 1.319584-2.111214 C -3.460905-3.703577 0.891606 C -11.032020-0.647936-1.496972 N -6.822145-1.441159-0.290140 H -11.472593-0.584339-0.489790 C -5.822431-1.690500-1.161859 H -11.732824-1.209874-2.142310 H -5.917929-1.249497-2.152545 C -9.344496-1.982371-2.696007 C -4.715593-2.453403-0.822800 H -8.390492-2.505372-2.586188 H -3.927179-2.616233-1.554811 H -9.238149-1.179410-3.430131 C -4.618121-2.990257 0.475547 H -10.113825-2.690482-3.035985 C -5.686109-2.754239 1.362627 C -9.936199-2.528997-0.408377 H -5.669496-3.152740 2.374991 H -9.028479-3.136086 0.367014 C -6.755100-1.975126 0.947674 H -10.776062-3.157363-0.738346 H -7.582661-1.754706 1.619620 H -10.155299-2.116934 0.580900 C 9.417702 1.964278-2.676475 N 6.803215-1.392630-0.221314 H 8.471733 2.506494-2.592247 C 5.832521-1.712916-1.102935 H 9.312994 1.161216-3.410521 H 5.948453-1.331387-2.115821 H 10.209224 2.655780-2.999432 C 4.731841-2.476702-0.748989 N 9.729617-1.474688-1.241400 H 3.967112-2.698364-1.490595 C 9.180441-2.582044-2.069379 C 4.610686-2.942270 0.574709 H 8.453859-3.150280-1.483359 C 5.647572-2.631005 1.474870 H 10.000926-3.246956-2.375348 H 5.611550-2.971166 2.507830 H 8.697010-2.164316-2.957171 C 6.711890-1.853026 1.043589 C 11.049937 0.607828-1.422279 H 7.514207-1.573541 1.724264 H 11.788851 1.168488-2.025245 H 11.442014 0.519068-0.396864 H 10.720443-1.243099 0.627934 C 9.951213 2.509230-0.375130 H 11.075241-2.772281-0.233828 H 9.051203 3.128882-0.361744 C 2.438528-4.218365 1.353671 H 10.809193 3.124557-0.682289 C 3.457786-3.662275 0.991667 S7
H 10.135454 2.097132 0.621204 C 10.788744-0.753556-2.026920 C 10.292969-2.040873 0.015419 H 11.713069-1.361346-2.038362 H 9.495875-2.539171 0.573131 H 10.423918-0.664539-3.062233 Cartesian coordinates of [(en)pd(l)] 6+ 3 in DMSO C 1 symmetry -3587.63982237 hartree -3588.49491198 hartree (single-point) Pd 7.157848-7.473032-1.319185 H 4.448017 9.390299 1.088854 N 3.894579 8.259443-0.564903 N 7.040643-9.356398-2.186600 C 3.979305 7.071250-1.199403 H 7.171774-10.059564-1.429300 H 3.446850 6.986126-2.144801 H 6.106617-9.539821-2.604754 C 4.697571 6.003707-0.683546 N 9.023294-7.458370-2.231046 H 4.734543 5.063281-1.229442 H 8.960889-6.835862-3.063820 C 5.368497 6.151713 0.546178 H 9.760420-7.059259-1.615589 C 5.279678 7.399857 1.192999 N 7.405892-5.569178-0.504650 H 5.779788 7.572184 2.143830 C 8.075551-5.394383 0.653222 C 4.539280 8.416923 0.610722 H 8.485003-6.289065 1.118319 C 8.240160-4.145396 1.232566 C -8.091326 1.633921 0.668040 H 8.785937-4.052105 2.169216 C -9.104327 0.880053 1.292060 C 7.692092-3.012292 0.599987 H -9.494354 1.167778 2.266216 C 6.999882-3.210307-0.610897 C -9.602552-0.247463 0.656888 H 6.558344-2.371227-1.144533 H -10.380260-0.854211 1.116722 C 6.880434-4.492261-1.124051 N 4.413823 10.669088-2.314273 S8
H 6.349085-4.677483-2.055742 H 4.979317 11.147099-1.581615 C 7.824543-1.715201 1.163331 H 5.030535 9.952692-2.747138 C 7.921917-0.601602 1.643191 N 1.772074 11.413781-2.270736 C 8.027126 0.701360 2.211317 H 1.235703 11.035871-3.079643 C 8.810750 0.916839 3.364643 H 1.078726 11.852624-1.632024 H 9.342044 0.079551 3.814178 N 1.024793 9.093856-0.480837 C 8.899960 2.191633 3.920662 C 0.616739 9.570183 0.714288 H 9.506936 2.351888 4.810547 H 1.236515 10.341339 1.167755 C 8.215337 3.262115 3.348331 C -0.529278 9.109164 1.344459 H 8.281398 4.257242 3.785073 H -0.818694 9.522055 2.308645 C 7.427943 3.062649 2.194661 C -1.301903 8.106513 0.726584 C 7.340417 1.779753 1.627844 C -0.864922 7.620556-0.521413 H 6.734230 1.619726 0.738413 H -1.423225 6.847276-1.044938 C 6.101127 5.077070 1.117114 C 0.291326 8.135983-1.085140 C 6.716196 4.150480 1.610036 H 0.655127 7.779659-2.047014 C 8.119983-9.493070-3.210583 C -2.477517 7.593100 1.336276 H 7.784966-8.966217-4.118445 C -3.481551 7.133587 1.846795 H 8.286862-10.555757-3.455151 C -4.653045 6.574765 2.435651 C 9.374173-8.848775-2.650816 C -5.193551 7.118553 3.619855 H 10.186653-8.832320-3.396911 H -4.712042 7.978726 4.082093 H 9.722590-9.388929-1.755893 C -6.333918 6.555141 4.189840 Pd 2.765242 9.821820-1.380718 H -6.747254 6.979743 5.103558 N -9.153639-0.654888-0.548953 C -6.947130 5.450134 3.601921 C -8.191149 0.065231-1.162319 H -7.835082 5.007459 4.050240 H -7.859496-0.295387-2.134155 C -6.418564 4.895621 2.417315 C -7.639062 1.202279-0.594244 C -5.272799 5.465076 1.836298 H -6.861520 1.748261-1.124410 H -4.860402 5.041400 0.922771 C -7.532164 2.783052 1.287947 C -7.197677-3.661579-1.195736 C -7.028768 3.759186 1.811002 H -7.074960-3.128211-2.136446 C 3.946630 11.656791-3.333215 C -5.315925-5.837931 1.162977 H 3.629987 11.090744-4.223953 C -4.415399-6.477120 1.673151 H 4.767983 12.337081-3.615353 C -3.355569-7.217360 2.273371 C 2.775540 12.416906-2.739125 C -3.584882-7.978236 3.439186 H 2.321771 13.099653-3.477390 H -4.582175-8.000870 3.875401 S9
H 3.095779 13.002151-1.862107 C -2.540709-8.692490 4.023857 Pd -9.916949-2.386252-1.439879 H -2.723876-9.278700 4.923194 N 5.248300-7.606308-0.478854 C -1.263299-8.660363 3.467519 C 4.197789-6.999386-1.069596 H -0.446871-9.216030 3.925885 H 4.402128-6.463491-1.994647 C -1.018222-7.903746 2.302138 C 2.918898-7.046667-0.537585 C -2.069728-7.185816 1.707454 H 2.101763-6.542491-1.049348 H -1.886809-6.600230 0.808696 C 2.694994-7.748999 0.662945 C 1.399368-7.814581 1.241008 C 3.800343-8.378735 1.267826 C 0.286276-7.859163 1.729751 H 3.686541-8.935168 2.195897 C -12.113216-2.234472-3.371490 C 5.048108-8.283911 0.670672 H -11.472435-2.179980-4.266280 H 5.921269-8.759316 1.113355 H -13.120934-1.868087-3.630966 N -11.497182-1.367954-2.321958 C -12.160070-3.651514-2.831880 H -12.191213-1.160966-1.573306 H -12.521168-4.362069-3.594627 H -11.205164-0.452715-2.719492 H -12.817989-3.709884-1.949836 N -10.780066-4.016743-2.390223 C -7.619523-4.959650 1.183259 H -10.188148-4.249923-3.214928 H -7.828645-5.457744 2.127745 H -10.795532-4.862592-1.785530 C -6.357792-5.077502 0.568424 N -8.399295-3.549774-0.592027 C -6.161803-4.407172-0.654963 C -8.602933-4.193391 0.577021 H -5.208735-4.465676-1.176503 H -9.586127-4.080267 1.029785 Cartesian coordinates of [(en*)pd(l)] 6+ 3 in DMSO. C 1 symmetry -4059.24758835 hartree -4060.20339077 hartree (single-point) S10
Pd 9.700790-2.490216-1.288137 C 6.167963 4.549661 2.967264 N -0.886340 9.210649-0.185601 C 6.606016 4.989625 4.233981 C -0.142337 8.265057-0.796809 H 7.444543 4.487820 4.714106 H -0.435330 7.994236-1.809549 C 5.966905 6.057492 4.861673 C 0.942693 7.663044-0.180378 H 6.309749 6.393223 5.839279 H 1.514170 6.905126-0.712205 C 4.890552 6.697097 4.249256 C 1.291397 8.041993 1.131197 H 4.389341 7.529052 4.741280 C 0.505167 9.028833 1.757466 C 4.441377 6.268628 2.982369 H 0.726349 9.359414 2.770272 C 5.086340 5.195496 2.344440 C -0.567317 9.580128 1.072870 H 4.744438 4.860691 1.367149 H -1.197411 10.339331 1.532897 C 2.394184 7.440752 1.793518 N 10.428258-4.203641-2.321833 C 3.338066 6.908798 2.346754 N 11.231427-1.439901-2.330551 C 11.323456-3.666473-3.402549 N 8.996048-0.775740-0.305222 H 10.676922-3.351463-4.236791 C 9.417250-0.461633 0.938121 H 11.983388-4.476409-3.766062 H 10.187945-1.099874 1.366649 C 12.138410-2.505505-2.878676 C 8.903308 0.614721 1.645316 H 12.765882-2.074111-3.681048 H 9.272652 0.828681 2.646231 H 12.801942-2.823948-2.059074 C 7.902044 1.413158 1.058196 Pd -2.578382 9.987154-1.147878 C 7.475369 1.075559-0.241343 N -7.314652-5.598467-0.405979 H 6.705716 1.657345-0.744313 C -6.716696-4.553734-1.015935 C 8.040395-0.015957-0.880722 H -6.219654-4.760894-1.961867 H 7.723494-0.306683-1.880719 C -6.727522-3.276385-0.478246 C 7.326627 2.514105 1.745949 H -6.232297-2.464085-1.006302 C 6.804012 3.453313 2.315789 C -7.378678-3.048641 0.750271 N -4.271829 10.798182-2.149804 C -7.997500-4.148788 1.375922 N -3.645224 8.368184-0.338224 H -8.514175-4.032380 2.326411 C -4.246554 8.468115 0.866489 C -7.940537-5.395332 0.772313 H -4.200456 9.439746 1.355005 C -8.402641-6.265473 1.235457 C -4.896391 7.398649 1.461692 N -1.523819 11.635895-1.985175 H -5.368569 7.526942 2.433570 C 6.970116-3.673251-0.830252 C -4.934830 6.156129 0.798455 H 6.831938-3.226727-1.813245 C -4.299576 6.064775-0.455472 C 5.927606-4.319047-0.185852 H -4.296452 5.130422-1.013006 H 4.953219-4.383132-0.665703 S11
C -3.670749 7.182346-0.982399 C 6.144834-4.884702 1.086154 H -3.168575 7.141559-1.947404 C 7.431684-4.760388 1.645208 C -5.590055 5.037650 1.377965 H 7.657571-5.175996 2.625124 C -6.153385 4.084794 1.882598 C 8.420723-4.096355 0.935420 C -6.816342 2.978808 2.489530 H 9.423412-3.981018 1.343441 C -7.494116 3.145527 3.716009 N -9.025033-7.439605-2.207695 H -7.506720 4.125369 4.190486 N -7.008480-9.486373-2.027390 C -8.139958 2.063430 4.310669 N -5.289035-7.644400-0.231189 H -8.661983 2.198350 5.256855 C -5.197878-8.061581 1.049863 C -8.121433 0.809533 3.703195 H -6.119901-8.402975 1.516966 H -8.624498-0.036990 4.167678 C -3.999422-8.061823 1.746445 C -7.447469 0.626693 2.476943 H -3.974819-8.407767 2.777802 C -6.797065 1.716207 1.872899 C -2.828618-7.607291 1.108293 H -6.275680 1.581474 0.927264 C -2.938582-7.174135-0.227709 C -7.404987-1.758414 1.342329 H -2.067433-6.813388-0.770659 C -7.422756-0.656677 1.857880 C -4.174554-7.206166-0.853764 C -2.437410 12.198620-3.037356 H -4.290522-6.873567-1.883798 H -2.324130 11.573492-3.937037 C -1.580329-7.576030 1.784241 H -2.115000 13.226233-3.289462 C -0.504996-7.532775 2.351417 C -3.867564 12.190717-2.546774 C 0.761150-7.467697 3.002417 H 4.553347 12.560376-3.332151 C 0.940863-8.025120 4.285898 H -3.985861 12.830843-1.658403 H 0.101827-8.512282 4.780000 Pd -7.148858-7.528413-1.205327 C 2.184250-7.951183 4.911357 N 8.199748-3.563242-0.285003 H 2.317492-8.384544 5.901530 C 3.258023-7.325497 4.280306 C -9.234079-6.170773-2.956693 H 4.228545-7.266247 4.770213 H -9.310154-5.339717-2.251397 C 3.093009-6.761455 2.997761 H -8.392382-6.006707-3.635685 C 1.841966-6.837888 2.362382 H -10.165352-6.241822-3.536729 H 1.709010-6.405428 1.372725 C -6.610945-10.515912-1.029493 C 5.095823-5.550575 1.773092 H -6.671033-11.511455-1.492146 C 4.179516-6.112199 2.343016 H -5.584316-10.331123-0.704143 C -8.999983-8.584078-3.182068 H -7.287217-10.469942-0.171055 H -8.410768-8.259287-4.054037 C -6.023026-9.489772-3.144890 H -10.030915-8.796923-3.522331 H -5.032050-9.248001-2.751268 S12
C -8.386809-9.805085-2.534108 H -5.997873-10.488401-3.604298 H -8.326551-10.642467-3.254345 H -6.306321-8.749341-3.897195 H -8.984345-10.138009-1.671070 C 9.351334-5.015092-2.950826 C -5.481015 10.873338-1.287034 H 8.742641-5.481415-2.172707 H -6.276053 11.410843-1.823692 H 8.727690-4.369212-3.575394 H -5.825990 9.863903-1.051692 H 9.806067-5.800031-3.572053 H -5.236539 11.408707-0.365095 C 11.195934-5.063052-1.377487 C -4.584117 9.975405-3.352586 H 10.523707-5.428912-0.596425 H -4.851918 8.963610-3.035760 H 11.618300-5.918476-1.924215 H -5.430914 10.425794-3.890152 H 12.004396-4.486518-0.920458 H -3.714703 9.931178-4.013419 C 12.022039-0.533648-1.455283 C -1.253694 12.650894-0.927951 H 12.858128-0.111667-2.031279 H -0.601696 12.213678-0.166834 H 11.383729 0.278359-1.098631 H -0.753872 13.520427-1.378531 H 12.412863-1.100187-0.605178 H -2.190870 12.969168-0.464368 C 10.629184-0.641860-3.435977 C -0.235071 11.246704-2.619937 H 9.969908 0.121109-3.013126 H 0.461191 10.904076-1.850873 H 11.430103-0.151246-4.007791 H -0.412778 10.446808-3.344587 H 10.054479-1.293746-4.098743 H 0.193225 12.119171-3.133956 H -11.093042-7.626022-1.758721 C -10.132558-7.607617-1.223893 H -10.005925-8.540864-0.669717 H -10.124235-6.765954-0.526367 S13
Figure S1. IR spectrum of [(en)pd(l)] 3 (OTf) 6 1t OTf (KBr, cm 1 ). S14
Figure S2. IR spectrum of [(en*)pd(l)] 2 (PF 6 ) 4 2d PF 6 (KBr, cm 1 ). S15
Figure S3. IR spectrum of {[(dppe)pd(l)](otf) 2 } 3 OTf (KBr, cm 1 ). S16
Figure S4. IR spectrum of [(en*)pd(l)] 3 [[ α-pw 12 O 40 ](NO 3 ) 3. S17
Figure S5. CSI-MS spectrum of {[(dppe)pd(l)](otf) 2 } 3 OTf (263 K, MeCN) S18
Figure S6. NMR spectra of [(en)pd(l)] 3 (OTf) 6 1t OTf in DMSO-d 6, (a) 1 H line (500 MHz), 13 C{H} line (124.50 MHz), and (c) 19 F line (465.89 MHz). S19
Figure S6. (Continued) S20
Figure S7. NMR spectra of [(en*)pd(l)] 2 (PF 6 ) 4 2d PF 6 in DMSO-d 6, (a) 1 H line (500 MHz), (b) 13 C{H} line (124.50 MHz), (c) 31 P{H} line (200.43 MHz), and (d) 19 F line (465.89 MHz). S21
Figure S7. (Continiued) S22
Figure S8. NMR spectra of {[(dppe)pd(l)](otf) 2 } 3 OTf in DMSO-d 6, (a) 1 H line (500 MHz), (b) 13 C{H} line (124.50 MHz), (c) 31 P{H} line (200.43 MHz) and (d) 19 F line (465.89 MHz). S23
Figure S8. (Continitued) S24
Figure S9. 1 H DOSY spectrum of [(en)pd(l)] n (OTf) 2n 1t/1d OTf (n = 2, 3) (DMSO-d 6, 303 K). S25
Figure S10. Curve fitting analysis of 1 H DOSY NMR for [(en)pd(l)] 3 (OTf) 6 1t OTf S26
Figure S11. Curve fitting analysis of 1 H DOSY NMR for [(en)pd(l)] 2 (OTf) 4 1d OTf. S27
Figure S12. Curve fitting analysis of 19 F DOSY NMR for [(en)pd(l)] n (OTf) 2n 1t/1d OTf (n = 2, 3). S28
Figure S13. 1 H DOSY spectrum of [(en*)pd(l)] n (PF 6 ) 2n 2t/2d PF 6 (n = 2, 3) (DMSO-d 6, 303 K). S29
Figure S14. Curve fitting analysis of 1 H DOSY NMR for [(en*)pd(l)] 2 (PF 6 ) 4 2t PF 6. S30
Figure S15. Curve fitting analysis of 1 H DOSY NMR for [(en*)pd(l)] 2 (PF 6 ) 4 2d PF 6. S31
Figure S16. Curve fitting analysis of 31 P DOSY NMR for [(en*)pd(l)] n (PF 6 ) 2n 2t/2d PF 6 S32
Figure S17. Curve fitting analysis of 1 H DOSY NMR for {[(dppe)pd(l)] 2 (OTf) 2 } 3 OTf. S33
Figure S18. Curve fitting analysis of 19 F DOSY NMR for {[(dppe)pd(l)] 2 (OTf) 2 } 3 OTf. S34
Figure S19. 1 H DOSY spectrum of [(en*)pd(l)] n (PF 6 ) 2n 2t/2d PF 6 (n = 2, 3) in the presence of H 3 [α-pw 12 O 40 ] (DMSO-d 6, 303 K). S35
Figure S20. Curve fitting analysis of 1 H DOSY NMR for {[(en*)pd(l)] 3 [[ α-pw 12 O 40 ]](PF 6 ) 3 2t [α-pw 12 O 40 ] 3. S36
Figure S21. Curve fitting analysis of 1 H DOSY NMR for {[(en*)pd(l)] 2 [α-pw 12 O 40 ]}(PF 6 ) 2d [α-pw 12 O 40 ] 3. S37
Figure S22. Curve fitting analysis of 31 P DOSY NMR for {[(en*)pd(l)] 3 [ α-pw 12 O 40 ]}(PF 6 ) 3 2t [α-pw 12 O 40 ] 3. S38
Figure S23. Curve fitting analysis of 31 P DOSY NMR for H 3 [α-pw 12 O 40 ]. S39
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