The linear oligomer 1 + SnCl 2 2 DPA G2

Transcription

1 Ymmoto_SI-figs,, 3, nd 4 DPA G + SnCl DPA G3 + SnCl DPA G SI-Figure. () UV-vis spectr of DPA G complexed with - equiv. of SnCl (solv.; dichloromethne/cetonitrile = :, [DPA G] = 9 x - M).. DPA G3 c d 36 nm 36 nm 3 nm DPA G + SnCl SI-Figure 3. UV-vis spectr of DPA G3 complexed with () -4, () -, (c) 3-6, (d) -4 equiv. of SnCl (solv.; dichloromethne/cetonitrile = :, [DPA G3] = x - M). The liner oligomer + SnCl DPA G. c. 344 nm 3 nm SI-Figure. UV-vis spectr of DPA G complexed with () -6, () -, (c) 3-6 equiv. of SnCl (solv.; dichloromethne/cetonitrile = :, [DPA G] = 3 x - M). The liner oligomer SI-Figure 4. UV-vis spectr of the liner oligomer complexed with -3 equiv. of SnCl (solv.; dichloromethne/cetonitrile = :, [the liner oligomer ] = x - M). S

2 Ymmoto_SI-figs, 6, nd The liner oligomer + SnCl DPA G4 + Eu(OTf) 3 The liner oligomer SI-Figure. () UV-vis spectr of the liner oligomer complexed with SnCl (Solv.; dichloromethne/cetonitrile = :, [the liner oligomer ] = 9 x - M). DPA G4 DPA G4 + L(OTf) 3 DPA-F G3 + SnCl.. c d 39 nm 366 nm 369 nm 3 4 DPA-F G SI-Figure 6. UV-vis spectr of DPA-F G3 complexed with () -, () -4, (c) -, (d) 3- equiv. of SnCl (solv.; dichloromethne/cetonitrile = :, [DPA-F G3] = x - M). DPA G4 SI-Figure. UV-vis spectr of () DPA G4 complexed with -3 equiv. of Eu(OTf) 3 nd () DPA G4 complexed with - equiv. of L(OTf) 3 (solv.; dichloromethne/cetonitrile = :, [DPA G4] = x -6 M). A SnCl molecule, which hs one coordintion site, is complexed with n imine site of DPAs t the rtio of :. On the other hnd, in the complextion of DPA G4 with Eu(OTf) 3, which hs multi coordintion sites, the spectrum chnged lrgel ddition of the smll mount of Eu(OTf) 3 to the solution of DPA G4 (SI-Figure ). This phenomenon shows tht Eu(OTf) 3 molecule is complexed with the severl imine sites of DPA G4. Therefore, stepwise complextion ws not confirmed, ut the spectrl chnge continued up to the ddition of 3 equivlents of Eu(OTf) 3. This result shows tht the complextion rndoml occurs nd the Eu slt is finll complexed with the imine site t the rtio of :. On the other hnd, in the complextion of DPA G4 with L(OTf) 3, the spectrum chnged up to the ddition of equivlents of L(OTf) 3 (SI-Figure ). The lrge metl size of L(OTf) 3 prevents the complextion due to the crowed interior of the dendrimer. S3

3 Ymmoto_SI-figs nd 9 MR spectr of DPA G nd the complex with SnCl DPA G4 full complexed with SnCl One molecule c nm nm d. nm Assemling structure of 4 equivlents of SnCl in DPA G4 SI-Figure. The MR spectr (4 Mz, dichloromethne-d/cetonitrile-d3 = :,.-6. onl) of () DPA G nd the complex with (), (c) 4, nd (d) 6 equiv. of SnCl. The mrked peks () re ttriuted to the four protons of the phenl group in the DPA G. In the spectrum of DPA G, singlet pek ttriuted to the four proton of the phenl ring ws shifted to lower mgnetic field dding of SnCl due to the coordintion to the imine nitrogens. The shift ws lrge up to equivlents ddition of SnCl, nd the shift ecme smller with the further ddition of SnCl. This spectrl chnge supports tht the complextion of SnCl first occurs t the imines in DPA G. Assemling structure of SnCl nm nm. nm SI-Figure 9. TEM pictures of () DPA G4 complexed with 3 equivlents of SnCl nd () DPA G4 complexed with 4 equivlents of SnCl (the smple ws inverted on RuO4 vpor for ver short time). The ssemling structure of 4 equivlents of SnCl in DPA G4 molecule ws oserved s round shpe with. nm dimeter s shown in SI-Figure 9 the TEM mesurement of DPA G4 complexed with 4 equivlents of SnCl (the smple ws inverted on RuO4 vpor for ver short time (within min)). This result directl supports tht 4 equivlents of SnCl molecules re complexed with the imine sites not t rndom ut stepwise up to the third shell of DPA G4. In genrl, the orgnic smples re inverted on RuO4 efore the TEM mesurement in order to enhnce the contrst of the imge, ut metl toms such s Sn pper on the TEM imge without or fter ver short time of the inversion. Therefore, the ssemling structure of SnCl in the dendrimer is confirmed the TEM mesurement of the complex. The DPA G4 molecule ws confirmed TEM to hve round shpe with.3 nm dimeter (Ref. ). The dimeter ws enhnced to. nm the complextion with 3 equivlents of SnCl (SI-Figure 9). As shown in SI-Figure 9, the. nm dimeter in the ssemling structure of 4 equivlents of SnCl in DPA G4 is smller thn tht in DPA G4. Therefore, The SnCl molecules were supported to e complexed with the imines not t rndom ut up to the third shell of the dendrimer. The dimeter of DPA G4 complexed wtih 4 equivlents of SnCl, which ws full inverted ( min), ws confirmed to e. nm, which shows the size of the complex. S4

4 Ymmoto_SI-figs nd Reduction of the imines in DPA G sed on the complextion with SnCl () Cl Sn DPA G + SnCl B 4 SnCl SnCl () DPA G trns cis trns cis (c) A min product otined reduction of DPA G complexed with equivlents of SnCl x x 6 SI-Figure. () Reduction of the imines in DPA G complexed with equivlents of SnCl. The MR spectr (4 Mz, DMSO-d 6 ) of () DPA G nd (c) the min product otined reduction of the complex. Reduction of imine onds is ccelerted the complextion with SnCl. DPA G with the reduced imines ws minl otined vi the reduction of DPA G complexed with equivlents of SnCl s shown in SI-Figure. In the spectrum of DPA G, two sets of peks (trns, cis) ttriuted to C-connected phenl rings pprer sed on the cis- or trns-conformtion for the phenl ring s shown in SI-Figure. On the other hnd, in the spectrum of the reduced product, onl one set of peks () ttriuted to C-connected phenl rings ppers due to the disppernce of the regio-conformtion, nd one pir of doulet peks (x, ) ttriuted to the reduced imines ppers round.3 s shown in SI-Figure c. Shell-selective reduction of the imines in DPA G sed on the stepwise complextion of SnCl () Cl Sn DPA G + SnCl B 4 SnCl SnCl () DPA G trnsa trnsb cisa cisb trns cis trnsa cisa trns cis cisb trnsb (c) A min product otined reduction of DPA G complexed with equivlents of SnCl trns cis trns cis x x cis 6 trns SI-Figure. () Selective reduction of the first shell of imines in DPA G complexed with equivlents of SnCl. The MR spectr (4 Mz, DMSO-d 6 ) of () DPA G nd (c) the min product otined reduction of the complex. Reduction of imine onds is ccelerted the complextion with SnCl. Therefore, the complextion sites of SnCl molecules inside DPA dendrimers re determined the identifiction of the product otined reduction of the complex. DPA G with the reduced imines of the first shell ws minl otined vi the reduction of DPA G complexed with equivlents of SnCl. This result strongl supports tht molecules of SnCl re complexed with the imines of the first shell of DPA G molecule s shown in SI-Figure. In the spectrum of DPA G, two sets of peks (trns, cis) ttriuted to the first shell of C-connected phenl rings pprer sed on the cis- or trns-conformtion for the phenl ring s shown in SI-Figure. On the other hnd, in the spectrum of the reduced product, onl one pir of doulet peks () ttriuted to C-connected phenl rings ppers due to the disppernce of the regio-conformtion, nd one pir of doulet peks (x, ) ttriuted to the reduced imines ppers round. s shown in SI-Figure c. S

5 Ymmoto_SI-fig Shell-selective reduction of imines in DPA G4 sed on the stepwise complextion of SnCl () DPA G4 + SnCl Cl Sn SnCl B 4 SnCl () DPA G4 Fixed conformtion (c) The product otined reduction of DPA G4-SnCl complex x x 6 SI-Figure. () Selective reduction of the first shell of imines in DPA G4 complexed with equivlents of SnCl. The MR spectr (4 Mz, DMSO-d 6 ) of () DPA G4, (c) the product otined reduction of DPA G4 complexed with equivlents of SnCl. Similrl to DPA G, DPA G4 with the reduced imines of the first shell ws otined vi the reduction of DPA G4 complexed with equivlents of SnCl s shown in SI-Figure. In the spectrum of DPA G4 (SI-Figure ), the protons do not pper s singlet pek due to the rigid conformtion of the fixed the ulk G4 dendrons (see ref. ). On the other hnd, singlet pek ttriuted to the protons ppers in the spectrum of the product otined reduction of DPA G4 complexed with equivlents of SnCl (SI-Figure c). This result supports tht molecules of SnCl re complexed with the imines of the first shell of DPA G4 molecule s shown in SI Figure. These results s shown in SI-Figures - directl supported tht SnCl is coordinted to the dendrimer not t rndom ut stepwise from the imines. S6