Synlett 2015; 26(19): 2659-2662
DOI: 10.1055/s-0035-1560207
letter
© Georg Thieme Verlag Stuttgart · New York

Design and Synthesis of new Nanosized C 3-Symmetrical Tricarboxylic Acids: Key Elongated Ligands for the Preparation of Highly Porous MOFs

Marios S. Markoulides*
Department of Chemistry, University of Cyprus, University Str. 1, Building No. 13, Aglantzia, 2109 Nicosia, Cyprus   Email: markoulides.marios@ucy.ac.cy   Email: nchronak@ucy.ac.cy
,
Constantinos G. Efthymiou
Department of Chemistry, University of Cyprus, University Str. 1, Building No. 13, Aglantzia, 2109 Nicosia, Cyprus   Email: markoulides.marios@ucy.ac.cy   Email: nchronak@ucy.ac.cy
,
Anastasios J. Tasiopoulos
Department of Chemistry, University of Cyprus, University Str. 1, Building No. 13, Aglantzia, 2109 Nicosia, Cyprus   Email: markoulides.marios@ucy.ac.cy   Email: nchronak@ucy.ac.cy
,
Nikos Chronakis*
Department of Chemistry, University of Cyprus, University Str. 1, Building No. 13, Aglantzia, 2109 Nicosia, Cyprus   Email: markoulides.marios@ucy.ac.cy   Email: nchronak@ucy.ac.cy
› Author Affiliations
Further Information

Publication History

Received: 03 July 2015

Accepted: 08 August 2015

Publication Date:
02 September 2015 (online)


Abstract

The synthesis of two new C 3-symmetrical nanosized tricarboxylic acids bearing triphenylmethane cores and three imines linkages is presented. The new elongated tripods were designed to stabilise highly porous metal-organic frameworks (MOFs) and were synthesized by a threefold Schiff base condensation reaction between the reduced leuco form of pararosaniline hydrochloride salt and an appropriate aldehyde.

Supporting Information

 
  • References and Notes

    • 1a Eddaoudi M, Moler DB, Li H, Chen B, Reineke TM, O’Keeffe M, Yaghi OM. Acc. Chem. Res. 2001; 34: 319
    • 1b Férey G. Chem. Soc. Rev. 2008; 37: 191
    • 1c Horike S, Shimomura S, Kitagawa S. Nat. Chem. 2009; 1: 695
    • 1d Bradshaw D, Claridge JB, Cussen EJ, Prior TJ, Rosseinsky MJ. Acc. Chem. Res. 2005; 38: 273
    • 2a Morris RE, Wheatley PS. Angew. Chem. Int. Ed. 2008; 47: 4966
    • 2b Rosi NL, Eckert J, Eddaoudi M, Vodak DT, Kim J, O’Keeffe M, Yaghi OM. Science 2003; 300: 1127
    • 2c Hayashi H, Côté AP, Furukawa H, O’Keeffe M, Yaghi OM. Nat. Mater. 2007; 6: 501
    • 2d Zheng S, Wu T, Zhang J, Chow M, Nieto RA, Feng P, Bu X. Angew. Chem. Int. Ed. 2010; 49: 5362
    • 2e Hasegawa S, Horike S, Matsuda R, Furukawa S, Mochizuki K, Kinoshita Y, Kitagawa S. J. Am. Chem. Soc. 2007; 129: 2607
    • 2f Neofotistou E, Malliakas CD, Trikalitis PN. Chem. Eur. J. 2009; 15: 4523
    • 2g Ma L, Falkowski JM, Abney C, Lin W. Nat. Chem. 2010; 2: 838
    • 2h Horcajada P, Serre C, Maurin G, Ramsahye NA, Balas F, Vallet-Regi M, Sebban M, Taulelle F, Férey G. J. Am. Chem. Soc. 2008; 130: 6774
    • 2i Chen B, Wang L, Zapata F, Qian G, Lobkovsky EB. J. Am. Chem. Soc. 2008; 130: 6718
    • 3a Furukawa H, Cordova KE, O’Keefe M, Yaghi OM. Science 2013; 341: 1230444
    • 3b Senkovska I, Kaskel S. Chem. Commun. 2014; 50: 7089
    • 3c Furukawa H, Ko N, Go YB, Aratani N, Choi SB, Choi E, Yazaydin AÖ, Snurr RQ, O’Keeffe M, Kim J, Yaghi OM. Science 2010; 329: 424
    • 3d Farha OK, Yazaydin AÖ, Eryazici I, Malliakas CD, Hauser BG, Kanatzidis MG, Nguyen ST, Snurr RQ, Hupp JT. Nat. Chem. 2010; 2: 944
    • 3e Farha OK, Eryazici I, Jeong NC, Hauser BG, Wilmer CE, Sarjeant AA, Snurr RQ, Nguyen ST, Yazaydin AÖ, Hupp JT. J. Am. Chem. Soc. 2012; 134: 15016
    • 3f Zheng B, Bai J, Duan J, Wojtas L, Zaworotko MJ. J. Am. Chem. Soc. 2011; 133: 748
    • 3g Manos MJ, Kyprianidou E, Papaefstathiou GS, Tasiopoulos AJ. Inorg. Chem. 2012; 51: 6308
    • 3h Efthymiou CG, Kyprianidou EJ, Milios CJ, Manos MJ, Tasiopoulos AJ. J. Mater. Chem. A 2013; 1: 5061
  • 4 Manos MJ, Markoulides MS, Malliakas CD, Papaefstathiou GS, Chronakis N, Kanatzidis MG, Trikalitis PN, Tasiopoulos AJ. Inorg. Chem. 2011; 50: 11297
  • 5 Duxbury DF. Chem. Rev. 1993; 93: 381
  • 6 Houjou H, Koga T, Akiizumi M, Yoshikawa I, Araki K. Bull. Chem. Soc. Jpn. 2009; 82: 730
  • 7 4,4′,4′′-Triaminotriphenylmethane (5) was prepared according to a literature procedure.6 Purification was performed by column chromatography on silica gel (acetone–Et3N = 9:0.08) to afford product 5 as a greyish-pink solid (52%);6 mp 210 °C (dec.). Rf  = 0.65 (acetone–Et3N = 9:0.08). IR (ATR): νmax = 3468 (br w), 3427 (br w), 3377 (br w), 3348 (br w), 3211 (br w), 3011 (w), 2357 (w), 2318 (w), 1622 (m), 1510 (s), 1435 (w), 1273 (m), 1176 (m), 1122 (w), 1084 (w), 1016 (w), 827 (m), 779 (m). cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 6.70 (6 H, d, J = 8.1 Hz, CH arom.), 6.44 (6 H, d, J = 8.1 Hz, CH arom.), 4.97 (1 H, s), 4.83 (6 H, s, 3 × NH2). 13C NMR (125 MHz, DMSO-d 6): δ = 146.17 (C arom.), 132.78 (C arom.), 129.14 (CH arom.), 113.51 (CH arom.), 53.80 (CH). HRMS (TOF MS AP+): m/z [M + H]+calcd for C19H20N3: 290.1657; found: 290.1652. UV/vis (DMSO): λmax (ε/dm3 mol–1 cm–1): 259 nm (34792), 298 nm (8418).
  • 8 Synthesis of 4,4,4′′-{[Methanetriyltris(benzene-4,1-diyl)-tris(azanylylidene)]tris(methanylylidene)}tribenzoic Acid (4a) A solution of 4-formylbenzoic acid (6, 189 mg, 1.25 mmol) in absolute EtOH (15 mL) was added into a stirred solution of 4,4′,4′′-triaminotriphenylmethane (5, 110 mg, 0.38 mmol) in absolute EtOH (40 mL), in a predried 100 mL single-neck round-bottomed flask equipped with a magnetic stirrer. The resulting mixture was stirred for seven days at r.t., under an atmosphere of dry nitrogen. The reaction mixture was then filtered under suction on a sintered funnel to give a greyish pink solid which was washed with absolute EtOH (60 mL). Purification of the solid was performed by column chromatography on silica gel (CHCl3–MeOH–Et3N = 9:1:0.15) to afford product 4a as a grey solid (232 mg, 89%); mp 237 °C (dec.). Rf  = 0.38 (CHCl3–MeOH–Et3N = 9:1:0.15). IR (ATR): νmax = 2991 (br w), 2879 (br w), 2667 (br w), 2540 (br w), 2358 (br), 2328 (br), 1691 (s), 1624 (m), 1570 (w), 1500 (m), 1421 (m), 1286 (s), 1196 (m), 1172 (w), 1112 (w), 1014 (m), 958 (w), 889 (w), 856 (w), 839 (w), 771 (s) cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 13.08 (3 H, br s, 3 × CO2H), 8.74 (3 H, s, N=CH), 8.06 (12 H, app. q, J = 7.9 Hz, CH arom.), 7.31 (6 H, d, J = 8.2 Hz, CH arom.), 7.23 (6 H, d, J = 8.2 Hz, CH arom.), 5.76 (1 H, s, CH). 13C NMR (125 MHz, DMSO-d 6): δ = 166.84 (CO2H), 159.61 (N=CH), 149.20 (C arom.), 142.13 (C arom.), 139.65 (C arom.), 132.87 (C arom.), 129.84 (CH arom.), 129.69 (CH arom.), 128.62 (CH arom.), 121.26 (CH arom.), 54.42 (CH). HRMS (TOF MS AP+): m/z [M + H]+ calcd for C43H32N3O6: 686.2291; found: 686.2323. UV/vis (DMSO): λmax (ε/dm3 mol–1 cm–1): 260 nm (79873), 344 nm (25047).
  • 9 Synthesis of 4-Formyl-(1,1-biphenyl)-4-carboxylic Acid (8) NaOH (497 mg, 12.4 mmol) was added into a stirred solution of methyl 4-(4-formylphenyl)benzoate (7, 2.13 g, 8.9 mmol) in MeOH–H2O (3:1, 500 mL) in a 1000 mL single-neck round-bottomed flask, and the resulting mixture was stirred at an elevated temperature of 55–60 °C for two weeks. During this time the consumption of the starting material was monitored by means of TLC (hexane–EtOAc = 4:1). Upon completion, MeOH was evaporated under reduced pressure, and 1 M NaOH (25 mL) was added. The aqueous solution was washed with EtOAc (3 × 150 mL) and finally made acidic with 3 M HCl. The precipitate was then filtered under suction on a sintered funnel to give an off-white solid which was washed successively with water, CHCl3, MeCN, and finally with Et2O. Residual solvent traces were removed under high vacuum to afford product 8 as an off-white solid (1.54 g, 77%). IR (ATR): νmax = 3072 (br), 3043 (br), 2951 (m), 2372 (w), 1713 (m), 1682 (m), 1603 (s), 1558 (w), 1425 (w), 1404 (w), 1296 (m), 1247 (m), 1219 (m), 1172 (w), 1113 (w), 1007 (m), 827 (s) cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 13.10 (1 H, br s, CO2H), 10.08 (1 H, s, CHO), 8.07–8.02 (4 H, m, 4 × CH arom.), 7.98 (2 H, d, J = 8.0 Hz, 2 × CH arom.), 7.90 (2 H, d, J = 8.0 Hz, 2 × CH arom.). 13C NMR (125 MHz, DMSO-d 6): δ = 192.72 (CHO), 166.90 (CO2H), 144.55 (C arom.), 142.78 (C arom.), 135.54 (C arom.), 130.53 (C arom.), 130.11 (CH arom.), 129.96 (CH arom.), 127.67 (CH arom.), 127.28 (CH arom.). HRMS (TOF MS AP+): m/z [M + H]+ calcd for C14H11O3: 227.0708; found: 227.0713. UV/vis (DMSO): λmax (ε/dm3 mol–1 cm–1): 252 nm (13111), 295 nm (21370).
  • 10 Synthesis of 4′,4′′′,4′′′′′-{[Methanetriyltris(benzene-4,1-diyl)tris(azanylylidene)]tris(methanylylidene)}tris(1,1′-bi-phenyl)-4′-carboxylic Acid (4b) A solution of 4′-formyl-(1,1′-biphenyl)-4-carboxylic acid (8, 203 mg, 0.89 mmol) in absolute EtOH (15 mL) was added into a stirred solution of 4,4′,4′′-triaminotriphenylmethane (5, 78.6 mg, 0.27 mmol) in absolute EtOH (35 mL), in a dry 100 mL single-neck round-bottomed flask. The resulting mixture was stirred for 10 d at r.t., under an atmosphere of dry nitrogen. The reaction mixture was then filtered under suction on a sintered funnel to give an off-white solid which was washed successively with EtOH, CHCl3, MeCN, THF, and finally with Et2O. Residual solvent traces were removed under high vacuum to afford product 4b as an off-white solid (157 mg, 63%). IR (ATR): νmax = 2989 (br w), 2871 (br w), 2656 (br w), 2543 (br w), 2362 (br), 1697 (s), 1610 (m), 1571 (w), 1510 (m), 1413 (m), 1364 (w), 1298 (s), 1199 (m), 1168 (w), 1117 (w), 1015 (w), 962 (w), 857 (w), 838 (w), 786 (m) cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 13.06 (3 H, br s, 3 × CO2H), 8.72 (3 H, s, N=CH), 8.04 (13 H, br s, 13 × CH arom.), 7.90 (13 H, br s, 13 × CH arom.), 7.31 (5 H, br s, 5 × CH arom.), 7.25 (5 H, br s, 5 × CH arom.), 5.76 (1 H, s, CH). 13C NMR (125 MHz, DMSO-d 6): δ = 167.04 (CO2H), 159.83, 159.56, 149.53, 143.24, 141.88, 141.58, 135.82, 129.99, 129.82, 129.29, 127.33, 126.92, 121.19, 66.98 (CH). HRMS (MALDI TOF, positive mode, reflectron, HCCA matrix on Prespotted AnchorChip PAC II 384/96): m/z [M + H]+ calcd for C61H44N3O6: 914.3225; found: 914.3221. UV/vis (DMSO): λmax (ε/dm3 mol–1 cm–1): 258 nm (57011), 303 nm (77785), 351 nm (37277).