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1 Supplemental Information Template-controlled Face-to-Face Stacking of Olefinic and Aromatic Carboxylic Acids in the Solid State Xuefeng Mei, Shuanglong Liu and Christian Wolf* Department of Chemistry, Georgetown University, Washington, DC 7 cw7@georgetown.edu Synthesis of,8-bis( -pyridyl)naphthalene.,8-diiodonaphthalene (. g,.8 mmol), -trimethylstannylpyridine (. g,. mmol), and tetrakis(triphenylphosphane)palladium() ( mg,. mol%) were dissolved in ml of anhydrous DMF and refluxed for hours. The reaction mixture was allowed to cool to room temperature, poured into % H OH, and extracted with CH Cl. The combined organic layers were washed with water, dried over MgSO and solvents were removed in vacuo. Recrystallization from EtOAc gave ( mg,. mmol, 7%) as light yellow crystals (mp 79-8 o C). H MR: δ.9 (dd, J =.7 Hz, J =. Hz, H), 7. (dd, J =. Hz, J = 7. Hz, H), 7. (dd, J =. Hz, J = 8. Hz, H), 8. (dd, J = 7. Hz, J = 8. Hz, H), 8. (dd, J =.7 Hz, J =. Hz, H). C MR: δ.,., 8., 9.7,.,., 7., 8.8,.. EI-MS (7 ev): m/z (%) = 8 () [M + ], () [M + -CH ], (9) [M + - CH ], () [M + -H, -Py], 7 () [M + - H, -Py]. Anal. Calc. for C H : C, 8.; H,.;, 9.9. Found: C, 8.; H,.8;, 9.9. SnMe + I I Pd(PPh ) Scheme. Synthesis of,8-bis(, -dipyridyl)naphthalene,.

2 Figure. H and C MR spectra of Cocrystallization and X-ray Diffraction. Single crystal X-ray analysis was performed at -87 o C using a Siemens platform diffractometer with graphite monochromated Mo-Kα radiation (λ =.77 Å). Data were integrated with the Siemens SAIT program and corrected using SADABS. The structures were solved by direct methods and refined with full-matrix least-square analysis using SHELX-97- software. on-hydrogen atoms were refined with anisotropic displacement parameters and all hydrogen atoms were placed in calculated positions and refined with a riding model. Crystallographic data have been deposited at the Cambridge Crystallographic Data Center: CCDC7 ( ), CCDC ( ), CCDC ( ), CCDC89 ( ), and CCDC 97 (). These data can be obtained free of charge at or from the Cambridge Crystallographic Data

3 Center, Union Road, Cambridge CB EZ, UK; Fax: +--; HO C HO C CO H HO C CO H HO C Figure. Structures of template and dicarboxylic acids -. CO H CO H A cocrystal of and was obtained by slow evaporation of a solution of,8- dipyridylnaphthalene (. g,. mmol) and fumaric acid (. g,. mmol) in ml of ethanol. Crystal structure data for cocrystal : Formula C H 8 O, M = 98., crystal dimensions. x. x. mm, monoclinic, space group P /c, a =.8() Å, b =.99() Å, c =.() Å, β =.7(), V = 99. Å, Z =, ρ calcd =.8 g cm -. H O C H H O O C H O Figure. Structure of. Selected crystallographic separations [Å] and angles [º]: -.99, H.79, H O.7, H.89, H O., H-O 7.8, H-O 7., C-H O 7.89, C-H O 9.8. A cocrystal of and was obtained by slow evaporation of a solution of,8- dipyridylnaphthalene (. g,. mmol) and terephthalic acid (8 mg,. mmol) in ml of ethanol. Crystal structure data for cocrystal : Formula C 8 H 8 O, M =., crystal dimensions. x. x. mm, monoclinic, space group C/c, a =.99(), b = 7.7(), c =.() Å, β =.878(), V = 9.8() Å, Z = 8, ρ calcd =.9 g/cm. C H O H O C H O H O Figure. Structure of. Selected crystallographic separations [Å] and angles [º]: -.77, H.8, H.98, H O., H O.7, -H-O 7.9, -H-O 7., C-H-O.98, C-H-O.. A cocrystal of and was obtained by slow evaporation of a solution of,8- dipyridylnaphthalene (. g,. mmol) and,-naphthalenedicarboxylic acid (7 mg,

4 . mmol) in ml of ethanol. Crystal structure data for cocrystal : Formula C H O, M = 98., crystal dimensions. x. x. mm, monoclinic, space group P /c, a =.78(), b =.8(), c = 8.() Å, β =.9(), V =7.8() Å, Z = 8, ρ calcd =. g/cm. C H O C H O H O H O Figure. Structure of. Selected crystallographic separations [Å] and angles [º]: -.9, H.78, H.89, H O.789, H O.78, -H-O 8., -H-O 7.7, C-H-O., C-H-O.. A cocrystal structure of and was obtained by slow evaporation of a solution of,8- dipyridinenaphthalene (. g,. mmol) and,-naphthalenedicarboxylic acid (7 mg,. mmol) in ml of ethanol. Crystal structure data for cocrystal : Formula C H O 8, M = 997., crystal dimensions. x. x. mm, monoclinic, space group C/c, a =.8(), b = 7.7(8), c =.7() Å, β = 7.7(), V = 8.(9) Å, Z =, ρ calcd =.7 g/cm. H O C H O H O C H O Figure. Structure of. Selected crystallographic separations [Å] and angles [º]: -.799, H.8, H.8, H O.8, H O.7, -H-O 77., -H-O 7.7, C-H-O 8.7, C-H-O.. Solid-state Reaction. A finely powdered crystalline sample of was placed in a quartz tube under and subjected to UV irradiation ( W, medium pressure wide band mercury lamp) for 7 hours. The sample was ground every 8 hours to ensure homogeneous irradiation. After completion of the reaction, the irradiated sample was separated between water and methylene chloride to recover the template. Freeze-drying of the aqueous phase afforded as a white solid. A single crystal of was prepared by slow evaporation of solution of the photoproduct in water. Cyclobutane-,,,-tetracarboxylic acid. H MR ( MHz, D O) δ =.7 (s, H). C MR (7 MHz, D O) δ =., 7.. Crystal data for : Formula C 8 H O, M = 8.8, crystal dimensions. x. x. mm, monoclinic, space group P /c, a =.8(), b =.(), c =.() Å, β =.98(), V = 9.() Å, Z =, ρ calcd =. g/cm.

5 C C HO C CO H C C HO C CO H Figure 7. Structure of. Selected crystallographic separations [Å] and angles [º]: C-C., C-C.7, C-C., C-C., C-C-C 89.98, C-C-C 89.7, C- C-C 88.8, C-C-C Figure 8. H and C MR spectra of. 7 References () Wolf, C.; Ghebremariam, B. T. Synthesis,, () Braga, D.; Benedi, O.; Maini, L.; Grepioni, F. J. Chem. Soc., Dalton Trans. 999, -8.