A Co-Crystal Strategy to Tune the Supramolecular Patterns and Luminescent Properties: Ten Well-Designed Salts Assembled by Arenedisulfonic Acid with Diverse Diamines

Ten salts assembled by arenedisulfonic acid with hydrazine, flexible aliphatic diamines, rigid and semirigid aromatic diamines, namely, (H 2 HA) 2+ ·(NDS) 2– ( 1 ), (H 2 EDA) 2+ ·(NDS) 2– ( 2 ), (H 2 PDA) 2+ ·(NDS) 2– ( 3 ), (H 2 BTDA) 2+ ·(NDS) 2– ( 4 ), (H 2 BDMA) 2+ ·(NDS) 2– ·2H 2 O ( 5 ), 2( o -HBDA) + ·(NDS) 2– ( 6 ), ( m -H 2 BDA) 2+ ·(NDS) 2– ( 7 ), (H 2 MBDA) 2+ ·(NDS) 2– ·3H 2 O ( 8 ), (H 2 SDA) 2+ ·(NDS) 2– ·H 2 O ( 9 ), and 2(HSDA) + ·(NDS) 2– ·H 2 O ( 10 ) (H 2 NDS = 1,5-naphthalenedisulfonic acid, HA = hydrazine, EDA = 1,2-ethanediamine, PDA = 1,3-propanediamine, BTDA = 1,4-butanediamine, BDMA = 1,3-benzenedimethanamine, o -BDA = 1,2-benzenediamine, m -BDA = 1,3-benzenediamine, MBDA = 4-methyl-1,3-benzenediamine, SDA = 4,4′-sulfonyldiamiline), have been constructed and characterized by elemental analysis, infrared, thermogravimetric analysis, phospholuminescence, and powder and single-crystal X-ray diffraction. Structural analyses indicate that the nature of the diamines can effectively influence the final structures of the salts through diverse noncovalent bonding interactions, such as hydrogen bonds, π···π stacking, N–H···π, C–H···π, and lone pair···π interactions, which result in six types of architectures. Crystals 1 – 3 exhibit a three-dimensional (3-D) pillared layered supramolecular network with the diammonium cations being sandwiched among the sulfonate groups, while crystal 4 exhibits a 3-D “honeycomb” network with the −(CH 2 ) 4 – groups being encapsulated among the NDS 2– anions. In comparison with crystal 4, crystals 5, 7, and 8 exhibit a different 3-D supramolecular network, in which the phenylene, phenyl, and methylphenyl groups interpenetrate with the naphthyl rings of NDS 2– anions through continuous π···π interactions. Crystal 6 is two-dimensional pillared layered network with the o -HBDA + cations arranging along the two sides of the layer. Crystal 9 possesses an organic 3-D supramolecular network formed by the C–H···π and sulfonyl involved lone pair···π interactions which encapsulates a one-dimensional (1-D) infinite [−SO 3 ···H 3 N−] n nanotube in the large voids. By contrast, crystal 10 possesses an organic 3-D supramolecular network formed by intricate C–H···π, π···π, and sulfonyl involved C/N–H···O interactions which encapsulates 1-D “centipede-shaped” [−SO 3 ···H 3 N−] n chains in the large voids. Luminescent investigations demonstrate that the salts containing aliphatic diamines exhibit stronger emission intensity than those containing aromatic diamines. This result indicates that the H 2 NDS might be used to distinguish the aliphatic diamine from aromatic diamine qualitatively through the luminescent signal.