Two-Component Supramolecular Metallogels with the Presence of Pt---Pt Metal Metal Interactions

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1 Electronic Supplementry Mteril (ESI) for Chemicl Communictions. This journl is The Royl Society of Chemistry 2018 Two-Component Suprmoleculr Metllogels with the Presence of Pt---Pt Metl Metl Interctions Zongchun Go, Peter A. Korevr, Ruolei Zhong, Zehong Wu, nd Feng Wng * CAS Key Lbortory of Soft Mtter Chemistry, ichem (Collbortive Innovtion Center of Chemistry for Energy Mterils), Deprtment of Polymer Science nd Engineering, University of Science nd Technology of Chin, Hefei, Anhui (P. R. Chin), E-mil: drfwng@ustc.edu.cn. Institute for Molecules nd Mterils, Rdboud University, Heyendlseweg 135, 6525 AJ Nijmegen, The Netherlnds. Supporting Informtion Mterils nd Methods Self-ssembly behvior of 1 Self-ssembly behvior of 2 Co-ssembly behviors of complexes 1/2 nd 1/2b Synthetic routes to monomers 1 nd 2b Mthemticl curve fitting of the ssembling process S2 S3 S6 S7 S10 S15 1

2 1. Mterils nd Methods Copper iodide (CuI) ws regent grde nd used s received. [Pt(tpy)Cl](BF 4), 6-phenyl- 2,2 -bipyridine pltinum(ii) chloride [(N^N^C)PtCl], compounds 2, 3, nd 4 were synthesized ccording to the previously reported procedures. [S1 S3] Other regents nd solvents were employed s purchsed. 1 H NMR spectr were collected on Vrin Unity INOVA-300 or INOVA-400 spectrometer with TMS s the internl stndrd. 13 C NMR spectr were recorded on Vrin Unity INOVA- 300 spectrometer t 75 MHz. MALDI-TOF mesurements were recorded on Bruker Autoflex Speed spectrometer with DCTB s the mtrix. UV/Vis spectr were recorded on UV-1800 Shimdzu spectrometer. Stedy-stte emission spectr were recorded on FluoroMx-4 spectrofluorometer (Horib Scientific) nd nlyzed with n Origin (v8.1) integrted softwre FluoroEssence (v2.2). Fluorescence lifetime dt were cquired with 1MHz LED lser with the excittion pek t 455 nm (NnoLED-455). Lifetime dt were nlyzed with DtSttion v6.6 (Horib Scientific). Trnsmission electron microscope (TEM) imges were performed on Tecni G2 Spirit BioTWIN electron microscope (ccelertion voltge: 120 kv). Rheologicl experiments were performed by the TA ARG2 stress-controlled rheometer with 40 mm prllel plte geometry. Gel smple ws trnsferred onto the plte t 298 K. Oscilltory dynmic sher experiments were performed in the frequency rnge of rd/s, using constnt strin (0.2%) determined with strin sweep to lie within the liner viscoelstic regime. For preprtion of the co-ssembled smple in solution: since either 2 or 2b is totlly insoluble in polr MCH/DCE (95 : 5, v/v) or decne/dce (95 : 5, v/v), the diluted stock solution method is employed to prepre the co-ssembled smples 1/2 nd 1/2b. 2

3 Counts Counts 2. Self-ssembly behvior of MCH:DCE=95:5 (v:v) τ = ns b 10 3 MCH:DCE=95:5 (v:v) τ = ns Time/ns Time/ ns Figure S1. Photoluminescence lifetime decys of 1 [ M in MCH/DCE (95 : 5, v/v)] t () 588 nm nd (b) 612 nm. Accordingly, the verged lifetime is determined to be 54.2 ns. 3 b4 2 α gg 3 α gg DCE % DCE % Wvelength / nm Wvelength / nm Figure S2. Solvent-dependent UV Vis spectr of 1 t 303 K: () 0.30 mm; (b) 0.40 mm; in MCH/DCE (95 : 5, v/v). Arrows indicte the spectrl chnges upon incresing DCE frction. Inset: α gg s function of DCE frction for 1 (λ = 485 nm). Non-liner fitting of the normlized curve with the previously reported solvent-dependent equilibrium model. [S4] 3

4 ln(c T ) b α gg 2 α gg Temperture/K Temperture/K 0.2 c Wvelength / nm d Wvelength / nm 2 α gg Temperture / K Wvelength / nm /T e (K -1 ) Figure S3. Temperture-dependent UV Vis spectr of 1: () 0.10 mm; (b) 0.30 mm; (c) 0.40 mm in MCH/DCE (95 : 5, v/v). Arrows indicte the spectrl chnges upon incresing temperture. Inset: α gg s function of temperture for 1 (λ = 485 nm). Non-liner fitting of the normlized curve with the Meijer Schenning Vn-der-Schoot mthemticl model ffords the corresponding thermodynmic prmeters (Tble S1). [S5] (d) vn t Hoff plot fitting nd the corresponding thermodynmic vlues. The concentrtion ws mde dimensionless by dividing 1 M Wvelength / nm b α gg T e =(351.2±0.45) K h e =(40.7±3.72) kj mol Temperture/K Figure S4. () Temperture-dependent UV Vis bsorption spectr of 1 (0.20 mm) in decne/dce (95 : 5, v/v). Arrows indicte the spectrl chnges upon incresing temperture. (b) α gg s function of temperture for 1 (λ = 485 nm). Non-liner fitting of the normlized curve with the Meijer Schenning Vn-der-Schoot mthemticl model ffords the corresponding thermodynmic prmeters (Tble S1). [S5] 4

5 Tble S1. Thermodynmic prmeters of 1 in MCH/DCE (95 : 5, v/v) nd decne/dce (95 : 5, v/v) obtined by fitting the temperture-dependent UV Vis bsorption dt. Solvent Concentrtion [M] T e [K] h e [kj mol -1 ] MCH/DCE=95:5 4.0 x ± ± 9 MCH/DCE=95:5 3.0 x ± ± 0.38 MCH/DCE=95:5 2.0 x ± ± 0.46 MCH/DCE=95:5 x ± ± 0.82 Decne/DCE=95:5 2.0 x ± ± 3.72 H (vii) H c H b b 7.40 (vi) (v) 7.38 (iv) δ Hc (iii) 7.36 (ii) (i) Concentrtion / M Figure S5. () Prtil 1 H NMR spectr (300 MHz, CDCl 3, 298 K) of 1 t different monomer concentrtions (from 15.2 mm of i to 0.95 mm of viii). (b) Chemicl resonnces chnges of H c on 1. The romtic protons on the min lignd show upfield shifts upon incresing the concentrtion, suggesting the involvement of π-π stcking interctions. By treting the collected chemicl shift chnges of proton H c with the nonliner curve-fitting eqution, the ssocition constnt (K ) vlue of 1 is determined to be (15.8 ± 2.2) M -1 in d-chloroform. 5

6 Emission Intensity Self-ssembly behvior of b Wvelength/nm Wvelength/nm Figure S6. () UV Vis bsorption nd (b) fluorescent spectr of 2 in DCE. Inset: imges of the solution colors of 2 in DCE nd MCH/DCE (95 : 5, v/v). Since 2 is insoluble nd forms yellow suspension in polr solvent, the model compound 2c is further employed to study the spectroscopic behviors Wvelength/ nm Figure S7. () UV Vis bsorption of 2c in DCE (blck line) nd MCH/DCE (95 : 5, v/v) (red line). For 2c, the mximum MLCT/LLCT bsorption bnd is locted t 483 nm in DCE. When switching the solvent to polr MCH/DCE (95 : 5, v/v), those bnd displys hypochromic shift (λ mx= 467 nm). Hence, it is pprent tht the newly-formed spectroscopic bnds of 1/2 ( nm, Figure 2 in the min text) re not originted from the 2 selfssembly process. 6

7 δhb/ppm 4. Co-ssembly behviors of complexes 1/2 nd 1/2b 1 H NMR titrtion experiments were performed for complex 1/2. In detil, the initil concentrtion of 1 ws kept constnt t 2.00 mm, while concentrtion of 2 ws systemticlly vried. Tretment of the collected chemicl shifts on 1 vs the concentrtion of guest (C A) with non-liner lest-squres curve-fitting eqution ffords the ssocition constnts. Specificlly, for 1 : 1 host/guest complextion, the binding constnts re clculted ccording to the following eqution: (Eqution S1) δ 0 nd δ re the chemicl shifts for selected host proton with nd without the presence of the guest, respectively. [C 0] is the totl concentrtion of the host, whilst [C A] is the concentrtion of the guest. δ lim is the limiting vlue of chemicl shifts for selected host proton with the presence of excess guest. K is the binding constnt. In terms of 1/2, K vlue is determined to be (72.5 ± 14.5) M -1 in CDCl 3, by nonliner curve-fitting of the collected 1 H NMR resonnces of H nd H b (Figure S8b). H H b b [Acceptor] / M -1 Figure S8. () 1 H NMR titrtion spectr (300 MHz, CDCl 3, 298 K) of 1 t the concentrtion of 2.00 mm upon progressive ddition of 2. (b) Chemicl resonnces chnge for protons H b on 1 nd the nonliner curve fittings. The romtic protons on 1 disply upfield shifts upon ddition of 2, suggesting the involvement of donor cceptor CT interctions. 7

8 0.6 b α gg 0.8 α gg DCE % DCE Frction (f) c Wvelength/nm d Wvelength/nm 1.5 α gg 1.8 α gg DCE % DCE frction (f) Wvelength/nm Wvelength/nm Figure S9. Solvent-dependent UV Vis bsorption spectr of 1/2 t 303 K:() 0.10 mm, (b) 0.20 mm, (c) 0.30 mm nd (d) 0.40 mm in MCH/DCE (95 : 5, v/v). Arrows indicte the spectrl chnges upon incresing DCE frction. Inset: α gg s function of DCE frction for 1/2 (λ = 620 nm). Non-liner fitting of the normlized curve with the previously reported solvent-dependent equilibrium model. [S4] Tble S2. Thermodynmics of 1 nd 1/2 ssembling processes Complex σ m (kj/mol) ΔG 0 (kj/mol) ΔG f=5 (kj/mol) 1 04 ± ± ± ± 0.1 1/2 177 ± ± ± 0.3 1/2 b 4 ± 35.7 ± ± 0.4 () in DCE/MCH mixture. (b) in DCE/decne mixture. 8

9 G/P Wvelength / nm Figure S10. () UV Vis bsorbnce spectr of 2 : 1 mixture of 1 nd 2b (c = M for 1) in MCH/DCE (95 : 5, v/v) (red line) nd DCE (blck line). 1/2b disply similr UV Vis spectr to those of 1/2, indicting tht the lkyl crosslinking unit exerts minor effect on noncovlent complextion behviors. Inset: imges of the solution colors of 1/2 in DCE nd MCH/DCE (95 : 5, v/v). b c 200 nm 200 nm d nm G' of 1/2b G'' of 1/2b ω / rd s Figure S11. TEM imge of () 1, (b) 1/2 nd (c) 1/2b on crbon coted copper grid. (d) Storge modulus (G') nd loss modulus (G'') vlues of the gels derived from 1/2b in MCH/DCE (95 : 5, v/v). Inset: photogrphs of gel from 1/2b. 9

10 5. Synthetic routes to monomers 1 nd 2b 5.1 Synthesis of monomer 1 Compound 3 (393 mg, 0.60 mmol), [(N^N^C)Pt]Cl (230 mg, 0 mmol), CuI (9.50 mg, 5 mmol) nd NEt 3 (1.5 ml) were dissolved in 30 ml of CH 2Cl 2, nd stirred t room temperture for 12 hours. The mixture ws evported under reduced pressure, nd the residue ws purified by column chromtogrphy (lumin, CH 2Cl 2 s the eluent) to fford 1 s red solid (460 mg, 85%). 1 H NMR (300 MHz, CDCl 3, 298K) δ (ppm): 9.18 (d, J = 5.2 Hz, 1H), 8.04 (dd, J = 21.1, 5.6 Hz, 1H), 7.97 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 7.9 Hz, 1H), 7.78 (t, J = 8.0 Hz, 1H), 7.58 (d, J = 7.9 Hz, 1H), 7.51 (t, J = 7.0 Hz, 2H), 7.34 (d, J = 7.4 Hz, 1H), 7.17 (t, J = 7.0 Hz, 1H), 7.05 (t, J = 7.4 Hz, 1H), 6.79 (s, 2H), (m, 6H), 1.79 (dd, J = 14.1, 6.8 Hz, 6H), 1.46 (s, 6H), 1.26 (s, 48H), 0.86 (dd, J = 6.8, 3.2 Hz, 9H). 13 C NMR (75 MHz, CDCl 3, 298K) δ (ppm): , , , , , , , , , , , , , , , , , , , , 73.52, 69.07, 31.94, 30.38, 29.78, 29.72, 29.68, 29.48, 29.41, 29.38, 26.17, 22.70, HRESIMS: m/z clcd for [M + K] +, ; found , error 6.08 ppm. 10

11 Figure S12. 1 H NMR spectrum (300 MHz, CDCl 3, 298 K) of 1. Figure S C NMR spectrum (75 MHz, CDCl 3, 298 K) of 1 11

12 Figure S14. Electrospry ioniztion spectrum of Synthesis of 2b [Pt(tpy)Cl](BF 4) (432 mg, 0.60 mmol), compound 4 (8 mg, 0.25 mmol), CuI (7.60 mg, 4 mmol) nd NEt 3 (1.5 ml) were dissolved in 30 ml of CH 2Cl 2, nd stirred t room temperture for 24 hours. The mixture ws evported under reduced pressure, nd the residue ws purified by column chromtogrphy (lumin, CH 3OH/CH 2Cl 2, 100 : 1 v/v s the eluent) to fford 2b s red solid (388 mg, 92%). 1 H NMR (300 MHz, CDCl 3, 298K) δ (ppm): 9.15 (d, J = 6.0 Hz, 4H), 9.01 (s, 4H), 8.90 (d, J = 1.4 Hz, 4H), 7.57 (dd, J = 6.0, 1.7 Hz, 4H), 7.43 (d, J = 8.6 Hz, 4H), 6.85 (d, J = 8.7 Hz, 4H), 4.00 (t, J = 6.4 Hz, 4H), 1.84 (s, 4H), 1.66 (s, 18H), 1.52 (s, 40H). 13 C NMR (75 MHz, CDCl 3, 298K) δ (ppm): , , , , , , , , , , , , 95.04, 67.91, 37.85, 36.62, 30.83, 30.39, 29.19, HRESIMS: m/z clcd for [M 2BF 4] 2+, ; found , error 0.93 ppm. 12

13 Figure S15. 1 H NMR spectrum (300 MHz, CDCl 3, 298 K) of 2b. Figure S C NMR spectrum (75 MHz, CDCl 3, 298 K) of 2b. 13

14 Figure S17. Electrospry ioniztion spectrum of 2b. 14

15 6. Mthemticl curve fitting of the ssembling process In terms of 1, it dopts coopertive mechnism for the suprmoleculr ssembling process. To cquire the detiled thermodynmic prmeters for the self-ssembly process, Meijer Schenning Vn-der-Schoot model hs been employed to fit the melting curves. S3,S5 In detil, non-sigmoidl curve cn be obtined by plotting the frction of ggregted species (α gg) ginst temperture t 485 nm on the bsis of temperture-dependent UV Vis bsorption spectr experiments. The suprmoleculr polymeriztion cn be divided into two seprted steps: the nucletion nd elongtion regimes. In the elongtion regime, the frction of ggregted molecules φ n is described by Eq. S1: φ n = φ SAT {1 exp[( h e ) (T T e )/(R T e )]} (Eq. S1) In this eqution, h e denotes the moleculr enthlpy relese due to the non-covlent suprmoleculr polymeriztion, T nd T e stnd for the bsolute temperture nd elongtion temperture, respectively. R represents the universl gs constnt. φ SAT is prmeter tht is introduced to prevent the reltion φ n/φ SAT surpssing the vlue of one. In the nucletion regime, it mens tht t tempertures below the elongtion temperture T e. φ n is described by Eq. S2: φ n = K /3 exp [(2/3K /3 1) h e (T T e )/(R T e )] (Eq. S2) K is the dimensionless equilibrium constnt for the nucletion step t T e. It is pprent tht the dt points re ccurtely fitted over the whole temperture rnge. Depending on Eq. 1 nd 2 in the min text, similr fitting process cn be performed for the solvent-dependent UV-Vis experiments vi Mtlb R2016 softwre. 15

16 REFERENCES: S1. W. Lu, B.-X. Mi, M. C. W. Chn, Z. H., C.-M. Che, N. Zhu nd S.-T. Lee, J. Am. Chem. Soc., 2004, 126, S2. Y.-K. Tin, Y.-G. Shi, Z.-S. Yng nd F. Wng, Angew. Chem. Int. Ed. 2014, 53, S3. Z. Go, Z. Li, Z. Go nd F. Wng, Nnoscle, 2018, 10, S4. P. A. Korevr, C. Schefer, T. F. A. de Greef nd E. W. Meijer, J. Am. Chem. Soc., 2012, 134, S5. P. Jonkheijm, P. vn der Schoot, A. P. H. J. Schenning nd E. W. Meijer, Science, 2006, 313,