supporting information · 2009-02-23 · peaks as internal standard. ms (es) analyses were...

Supporting InformationCoquiere et al. 10.1073/pnas.0811663106SI TextMaterials and Methods1H and 13C NMR spectra were recorded either with a BrukerARX 250, Avance 500 apparatus or Varian 400 in CD3CN.Chemical shifts (�) are denoted in ppm using residual solventpeaks as internal standard. MS (ES) analyses were performedwith a Finnigan LCQ Advantage apparatus. Ligand 1NH2, 1NO2

and complex [Zn(1NH2)(L)](ClO4)2 were previously and fullycharacterized by our group (1, 2).One-dimensional and 2D 1H NMR experiments. 1H-NMR experimentswere recorded at 300 K on a Bruker ARX 250 spectrometer.Representative experimental conditions for acid titration byNMR: complex [Zn(1R)(H2O)](ClO4)2 or ligand 1R (5 mg) wasdissolved in CD3CN (0.5 ml). 1H NMR spectra were record aftereach addition of an aliquot of a stock solution containing 10 to20% of acid in CD3CN. Competitive binding: 3.5 equiv of a 1:1mixture of n-butylamine/1,3-propyldiamine diluted in CD3CNwere added to a CD3CN solution of complex[Zn(1NH2)(H2O)](ClO4)2 (8 mg, 0.5 ml) and a first 2D COSY 1HNMR spectrum was recorded (S7). Then, aliquots (0.5 equiv) ofpicric acid (diluted in CD3CN) were carefully added untilcomplete exchange of butylamine by 1,3-propyldiamine and asecond 2D COSY spectrum was recorded (Fig. S8).XRD. Compound [Zn(1NH2.H)(CH3CN)](ClO4)3 (3 mg) was dis-solved into a CH2Cl2/MeOH (8/2, 0.5 ml) solution. Slow diffu-sion of ether at room temperature gave crystals suitable forX-ray analysis after 4 days.

Colorless crystals (size 50 � 50 � 100 �m) of the complex[Zn(1NH2.H)(MeCN)]3� perchlorate were harvested from thecrystallization solution using a nylon cryoloop and rapidly frozenin liquid nitrogen. One crystal was mounted on the BM14beamline at the European Synchrotron Radiation Facility(ESRF) synchrotron (Grenoble, France). The crystals, based onmosaicity and the shape of diffraction spots were all found ofpoor quality. The best crystal we were able to select among alltested was used for recordings. The corresponding data collec-tion statistics are reported in Table S1. Intensities were pro-cessed using the HKL2000 program (3) best in the P63 spacegroup and converted to structure factors. The structure wassolved using SHELXS and refinements were carried out with theSHELXL program (4). The asymmetric unit consists of a thirdof the calixarene moiety, with the P63 crystallographic axisgenerating the complete molecule. The zinc atom and its coor-dinated water molecule O1W stand on this axis as well as theacetonitrile molecule within the cavity, in the opposite directionto O1W. However, the presence of complexed water and aceto-

nitrile molecules break the molecular 3-fold symmetry. In P63,the methyl group of acetonitrile was found disordered andslightly out of the P63 axis, and no hydrogen can be seen on O1W.Nevertheless, refinements were conducted and convergedreadily in the P63 space group, the acetonitrile being refined asa constrained system. In this space group, the terbutyl group ofone of the calixarene rings is observed rotating and was refinedas a rigid group with 2 (54:46) occupancies. The perchlorateanion was also found disordered around the central chlorineatom. This group was refined as a 2 alternate position group withthe sum of occupancies constrained to unity (this converged toa ratio 73:27). Most of the hydrogen atoms were located inFourier difference-maps but they were kept in calculated posi-tion with an isotropic thermal factor riding on that of the bondedcarbon, except for O1W and the anilino nitrogen atoms where nohydrogen was found. The cif file of the structure was depositedwith the Cambridge Crystallographic Data Centre (Cambridge,U.K.) with the reference number 623586.

Computational ModelingThe calculations have been performed at the Institut du Deve-loppement et des Ressources en Informatique Scientifique (ID-RIS) (F. 91403, Orsay, France) and the Centre InformatiqueNational de l’Enseignement Superieur (CINES) (F. 34000 Mont-pellier, France) national supercomputing centers as well as at theCentre de Calcul Recherche et Enseignement of the UniversityParis 6 (F. 75252, Paris, France).

We used our own implementation of the hybrid DFT/MMscheme by interfacing the Gaussian03 (5) suite of programs withthe DYNAMO Fortran library (6). The DFT computations aredone with the 6–31G** basis set and the B3LYP functional. Thevibrational frequencies are computed on every optimized struc-ture to confirm the nature of the geometries (energy minimum).We use the XRD structures as starting geometries of theindividual complexes. They were then solvated in a 55 � 55 �55-Å3 chloroform box with boundary conditions applied tosimulate a continuous medium. No counter ions were included.For the [Zn(1NH2.H)(MeCN)]3� complex the quantum partitionincludes the 3 aniline functions (-NH2) and the proton. Theremaining atoms (Calixarene, Zn(II), MeCN, a water moleculeand the solvent) are treated with molecular mechanics via theOptimized Potentials for Liquid Simulations Force Field (7). Forthe [Zn(1NH2)(NH2C3H6NH3)]3� complex, the 3 aniline func-tions and the ammonium group of the host molecule(-CH2NH3

�) are treated quantumly. For ease of computationthe solvent molecules situated beyond 15 Å of the calixarenecenter of mass are kept fixed during optimization.

1. Coquiere D, Marrot J, Reinaud O (2006) Encapsulation of a (H3O2)- unit in the aromaticcore of a calix[6]arene closed by 2 Zn(II) ions at the small and large rims. Chem Commun2006:3924–3926.

2. Redon S, Li Y, Reinaud O (2006) Unprecedented selective ipso-nitration of calixarenesmonitored by the O-substituents. J Org Chem 68:7004–7008.

3. Otwinowsky Z, Minor W (1997) Processing of X-ray diffraction data collected inoscillation mode. Methods Enzymol 276:307–326.

4. Sheldrick G, Schneider TR (1997) SHELXL: High resolution refinement. Methods Enzy-mol 277:319–341.

5. Pople JA, et al. (2003) (Gaussian, Inc., Pittsburgh PA, www.gaussian.com).6. Field MJ (1999) A Practical Introduction to the Simulation of Molecular Systems

(Cambridge Univ Press, Cambridge, UK).7. Jorgensen WL, Maxwell DS, Tirado-Rives J (1996) Development and testing of the OPLS

all-atom force field on conformational energetics and properties of organic liquids.J Am Chem Soc 118:11225–11236.

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Fig. S1. From bottom to top: Evolution of the 1H NMR spectra (300 K, 250 MHz) of a CD3CN solution containing complex [Zn(1NH2)(CD3CN)](ClO4)2 upon theprogressive addition of 1 equiv of HClO4 (dilute in CD3CN). �, tBu; E, OCH3; Œ, NCH3 and HIm; �, CH2Ar; F, CH2Im; �, HArNH2; ■ , HArtBu.



Fig. S2. From bottom to top: Evolution of the 1H NMR spectra (300 K, 250 MHz) of a CD3CN solution containing complex [Zn(1NH2)(CD3CN)](ClO4)2 upon theprogressive addition of a CD3CN solution of picric acid. �, tBu; E, OCH3; Œ, NCH3 and HIm; �, CH2Ar; F, CH2Im; �, HArNH2; ■ , HArtBu; ❖ , picrate.



Fig. S3. From bottom to top: Evolution of the 1H NMR spectra (300 K, 250 MHz) of a CD3CN solution containing complex [Zn(1NH2)(CD3CN)](ClO4)2 upon theprogressive addition of a CD3CN solution of TFA. �, tBu; E, OCH3; Œ, NCH3 and HIm; �, CH2Ar; E, CH2Im; �, HArNH2; ■ , HArtBu.



Fig. S4. Due to their specific location on the flexible calixarene core, the anilines act cooperatively and behave as more basic than the imidazole groups situatedat the small rim. (Left) From bottom to top: Evolution of the 1H NMR spectra (300 K, 250 MHz) of a CD3CN solution containing ligand 1NH2 upon the progressiveaddition of HClO4. �, tBu; E, OCH3; Œ, NCH3 and HIm; �, CH2Ar; ƒ, NH2; F, CH2Im; ■ , HArNH2; and �, HArtBu. (Right) Schematic representation of the correspondingspecies present in solution.



Fig. S5. From bottom to top: Evolution of the 1H NMR spectra (300 K, 250 MHz) of a CD3CN solution containing ligand 1NO2 upon the progressive addition ofa CD3CN solution of HClO4. �, tBu; E, OCH3; Œ, NCH3 and HIm; �, CH2Ar; F, CH2Im; �, HArNH2; ■ , HArtBu.



Fig. S6. From bottom to top: (Left) Evolution of the 1H NMR spectra (300 K, 250 MHz) of a CD3CN solution of complex [Zn(1NH2)(H2O)](ClO4)2 before (a), andafter (b) the addition of a 1:1 mixture of n-butylamine/1,3-propyldiamine (3.5 eq diluted in CD3CN), and after subsequent addition of aliquots (0.5 eq) of picricacid (HX diluted in CD3CN) (c–e). �, tBu; E, OCH3; Œ, NCH3 and HIm; �, CH2Ar; F, CH2Im; ■ , HArNH2, �, HArtBu; and ❖ , picrate. (Center) Enlargement of the up-fieldarea. (Right) Schematic representation of the corresponding species present in solution.



Fig. S7. COSY 1H NMR spectrum (250 MHz, CD3CN,300 K) of complex [Zn(1NH2)(NH2C4H9)]2ClO4 (matches the 1H NMR spectrum of Fig. S6B). �, �, �, and �,n-butylamine endo-coordinated; dotted lines, correlations.




Fig. S8. COSY 1H NMR spectrum (250 MHz, CD3CN,300 K) of complex [Zn(1NH2)(NH2C3H6NH3)]3� (matches the 1H NMR spectrum of Fig. S6E). �, �, and �, diaminemonoprotonated endocoordinated; dotted lines, correlations.




Fig. S9. Computed minimized structure of complex [Zn(1NH2.H)(MeCN)]3�. Selected interatomic distances (Å) and angles (°): Zn-NIm 2.045, 2.046, 2.051, (°):(Zn-NIm)av � 2.05, Zn-Nnitrilo 2.00, Nanilino

…Nanilino 3.023, 3.073, 4.374, NIm-Zn-NIm 118.9, 125.6, 113.9, NIm-Zn-Nnitrilo 93.03, 93.80, 96.05; dihedral angle N-Zn-N-N164.47.



Other Supporting Information Files

Table S1 (PDF)Table S2 (PDF)Table S3 (PDF)

Fig. S10. Computed minimized structure of complex [Zn(1NH2)(NH2C3H6NH3)]3�. Selected interatomic distances (Å) and angles (°): (Zn-NIm)av � 2.05, 2.03 and2.03, Zn-Namine 2.01, N-Zn-N 112.66, 107.84 and 104.71, NRNH3�

…NArNH2 2.96, 2.83 and 3.67, Namine…O 2.45 and 3.11.






supporting information · 2009-02-23 · peaks as internal standard. ms (es) analyses were...

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