Construction of right-handed-, left-handed- and racemic helical. coordination polymers. Enantioselective recognition via chiral.

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1 <Electronic Supplementry Informtion> Construction of right-hnded-, left-hnded- nd rcemic helicl coordintion polymers. Enntioselective recognition vi chirl helicl crystls Kyung Hwn Prk, Te Hwn Noh, Yoon-Bo Shim nd Ok-Sng Jung* Deprtment of Chemistry nd Chemistry Institute for Functionl Mterils, Pusn Ntionl University, Pusn , Kore Experimentl Mterils nd physicl mesurements. CuCl 2 ws purchsed from Strem Co., nd used s received. Elementl micronlyses (C, H, N) were performed on crystlline smples by KBSI Pusn Center using Vrio-EL III nlyzer. Therml nlyses were performed under N 2 t scn rte of 10 C/min using Lbsys TGA-DSC Infrred spectr were obtined on Nicolet 380 FT-IR spectrophotometer using smples prepred s nujol mulls nd KBr pellets. Cyclic voltmmogrms (CVs) were recorded using potentiostt/glvnostt, Kosentech model KST-P2. from to 0.10 V vs Ag/AgCl in 0.01 M PBS of ph 7.0. Synthesis of bis(4-pyridyl)methylvinylsilne (L). n-butyllithium (35 mmol, 2.5 M solution in n-hexne) ws dded dropwise to solution of 4-bromopyridine (33 mmol) in dry diethyl ether (60 ml) under nitrogen gs t 78 C, t which temperture the resulting mixture ws stirred for 1.5 h. At 0 C, dichloromethylvinylsilne (16 mmol) ws slowly

2 dded to the yellow suspension nd stirred for 12 h. Distilled wter (50 ml) ws dded into the rection solution, nd the orgnic solution lyer ws seprted. The orgnic solution ws wshed with wter, nd then ws dried over MgSO 4. The crude product ws purified by column chromtogrphy on silic gel with ethyl cette. The solvent ws evported to obtin viscous liquid in 63% yield. Anl. Clcd for C 13 H 14 N 2 Si: C, 68.98; H, 6.23; N, Found: C, 69.10; H, 6.20; N, H NMR (Me 2 SO-d 6, SiMe 4, δ): 8.59 (d, J = 5.7 Hz, 4H), 7.47 (d, J = 5.7 Hz, 4H), 6.55 (dd, J = 14.4 Hz, J = 20.4 Hz, 1H), 6.30 (dd, J = 3.6 Hz, J = 12.0 Hz, 1H), 5.88 (dd, J = 3.3 Hz, J = 20.4 Hz, 1H), 0.70 (s, 3H). IR (KBr, cm 1 ): 636 (s), 787 (s), 1124 (s), 1402 (s), 1583 (s). Synthesis of [CuCl 2 (L)(HCONMe 2 )]: A methnol solution (5 ml) of CuCl 2 (67 mg, 0.5 mmol) ws mixed with n ethnol solution (5 ml) of L (113 mg, 0.5 mmol), nd the resulting solid ws filtered nd dried in vcuum. Diethyl ether ws vpor-diffused into the N,N-dimethylformmide (HCONMe 2 ) solution of the crude product to obtin single crystls (consisting of rcemic helices) suitble for X-ry crystllogrphy. The single crystls were obtined in 3 dys in n 80% yield. Anl. Clcd for C 16 H 21 Cl 2 CuN 3 OSi: C, 44.29; H, 4.88; N, Found: C, 44.20; H, 4.78; N, IR (nujol mull, cm 1 ): 1686 (s, ν(co) of HCONMe 2 ), 1645(s), 1124(s), 800(s), 553(s). Synthesis of [CuCl 2 (L)(Me 2 SO)] Me 2 SO: A methnol solution (5 ml) of CuCl 2 (67 mg, 0.5 mmol) ws mixed with n ethnol solution (5 ml) of L (113 mg, 0.5 mmol), nd the resulting solid ws filtered nd dried in vcuum. Acetone ws vpor-diffused into the dimethyl sulfoxide (Me 2 SO) solution of the crude product to obtin two kinds of single crystls (consisting of P nd M helices) suitble for X-ry crystllogrphy. Single crystls were obtined in 4 dys in n 83% yield. Anl. Clcd for C 17 H 26 Cl 2 CuN 2 O 2 S 2 Si: C, 39.49; H, 5.07; N, Found: C, 40.10; H, 5.01; N, IR (nujol mull, cm 1 ): 1599 (m), 1411(s), 1012(s), 791(s), 723(s).

3 Crystllogrphic structure determintions. All X-ry dt were collected on Bruker SMART utomtic diffrctometer with grphite-monochromted Mo Kα rdition (λ = Å) nd CCD detector t mbient temperture. The 36 frmes of two dimensionl diffrction imges were collected nd processed to obtin the cell prmeters nd orienttion mtrix. Absorption effects were corrected by the multi-scn method. The structures were solved by the direct method (SHELXS 97) nd refined by full-mtrix lest squres techniques (SHELXL 97). 1 The non-hydrogen toms were refined nisotropiclly, nd hydrogen toms were plced in clculted positions nd refined using riding model. For [CuCl 2 (L)(HCONMe 2 )], the vinyl groups nd the methyl groups ttched to silicon tom were disordered. Also, solvent molecules in the voids were highly disordered nd were impossible to refine using conventionl discrete-tom models. Therefore, the residul electron density ws treted s diffuse contributions using the SQUEEZE of the PLATON softwre nd locted series of voids (see below). 2 _plton_squeeze_void_nr _plton_squeeze_void_verge_x _plton_squeeze_void_verge_y _plton_squeeze_void_verge_z _plton_squeeze_void_volume _plton_squeeze_void_count_electrons _plton_squeeze_void_content ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' '

4 ' ' ' ' ' ' Crystllogrphic dt for the structure reported here hve been deposited with the Cmbridge Crystllogrphic Dt Centre (Deposition No. CCDC , , nd for rcemic, P, nd M helices, respectively). The dt cn be obtined free of chrge vi (or from the CCDC, 12 Union Rod, Cmbridge CB2 1EZ, UK; fx: ; e-mil: deposit@ccdc.cm.c.uk). The crystl prmeters nd procedurl informtion regrding the dt collection nd structure refinement re given in Tble S1, nd relevnt bond lengths nd ngles re listed in Tble S2. References 1 Sheldrick, G. M. SHELXS-97: A Progrm for Structure Determintion; Universit y of Göttingen, Germny, 1997; Sheldrick, G. M. SHELXL-97: A Progrm for Structure Refinement; University of Göttingen, Germny, Spek, A. L. J. Appl. Crystllogr., 2003, 36, 7.

5 Het flow ( V) Weight (%) Het flow (W/g) TG (%) Electronic Supplementry Mteril (ESI) for Chemicl Communictions 100 TGA DSC Temperture ( o C) -1.5 (DSC) (TG) Temperture ( o C) Fig. S1 TGA nd DSC nlyses of [CuCl 2 (L)(HCONMe 2 )] (top) nd [CuCl 2 (L)(Me 2 SO)] Me 2 SO (bottom).

6 Cl2 Cu1 Cl1 N1 O1 S1 Si1 Cl1 O1 S1 Cl2 Cu1 N1 Si1 N2 N2 Fig. S2 ORTEP drwings of M-[CuCl 2 (L)(Me 2 SO)] Me 2 SO (left) nd P- [CuCl 2 (L)(Me 2 SO)] Me 2 SO (right).

7 c b b c b b Fig. S3 Pcking digrms of P-[CuCl 2 (L)(Me 2 SO)] Me 2 SO (top) nd M- [CuCl 2 (L)(Me 2 SO)] Me 2 SO (bottom).

8 c c Fig. S4 Schemtic representtion of rcemic crystl (top) nd P crystl (bottom).

9 Tble S1 Crystllogrphic dt for [CuCl 2 (L)(HCONMe 2 )] (rcemic), P- [CuCl 2 (L)(Me 2 SO)] 0.5Me 2 SO (right-hnded), nd M-[CuCl 2 (L)(Me 2 SO)] Me 2 SO (lefthnded). Rcemic P (right-hnded) M (left-hnded) formul C 32 H 41 Cl 4 Cu 2 N 6 O 2 Si 2 C 16 H 23 Cl 2 CuN 2 O 1.5 S 1.5 Si C 17 H 26 Cl 2 CuN 2 O 2 S 2 Si weight crystl system Cubic Tetrgonl Tetrgonl spce group I4 3 /d P4 1 P4 3, Å (4) (4) (2) b, Å (4) (4) (2) c, Å (4) (1) (3) V, Å (6) (2) (7) Z d cl, Mg m µ, mm R {I > 2σ(I)} R 1 = R 1 = R 1 = b wr 2 = wr 2 = wr 2 = flck χ prmeter 0.00(2) 0.01(2) 0.00(2) R 1 = F c F c / F o. b wr 2 = w(f 2 o F 2 c ) 2 / wf 4 o ) 1/2

10 Tble S2 Bond lengths [Å] nd ngles [ ] for [CuCl 2 (L)(HCONMe 2 )] (rcemic), P- [CuCl 2 (L)(Me 2 SO)] Me 2 SO (right-hnded), nd M-[CuCl 2 (L)(Me 2 SO)] Me 2 SO (left-hnded). Rcemic P (right-hnded) M (left-hnded) Cu1 N (4) Cu1 N (6) Cu1 N (4) Cu1 N (4) Cu1 N2 # (6) Cu1 N2 # (4) Cu1 Cl (1) Cu1 Cl (2) Cu1 Cl (2) Cu1 Cl (1) Cu1 Cl (3) Cu1 Cl (2) Cu1 O (3) Cu1 O (5) Cu1 O (4) N1 Cu1 N (2) N1 Cu1 N2 # (3) N1 Cu1 N2 # (2) C3 Si1 C3 # (3) C5 Si1 C (3) C5 Si1 C (2) C8 Si2 C8 # (3) #1 x, y+2, z+3/2 #2 x, y,z 1/4, # x 1, y+2,z+1/4