Ligand-Directed Molecular Architectures:  Self-Assembly of Two-Dimensional Rectangular Metallacycles and Three-Dimensional Trigonal or Tetragonal Prisms

Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L 1 , 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 2 , and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L 3 ) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylben...

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Published inJournal of the American Chemical Society Vol. 125; no. 28; pp. 8595 - 8613
Main Authors Su, Cheng-Yong, Cai, Yue-Peng, Chen, Chun-Long, Smith, Mark D, Kaim, Wolfgang, zur Loye, Hans-Conrad
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 16.07.2003
Amer Chemical Soc
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Abstract Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L 1 , 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 2 , and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L 3 ) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 4 have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures:  [Ag2 L 1 2](BF4)2 1, [Ag2 L 2 2](CF3SO3)2 2, [CF3SO3 - ⊂ Ag2 L 3 2]CF3SO3 3, [CF3SO3 - ⊂ Ag2 L 3 3]CF3SO3 4, [ClO4 - ⊂ Cu2 L 2 4](ClO4)3 5, [4H2O ⊂ Ni2 L 2 4Cl4]·6H2O 6, [BF4 - ⊂ Ag3 L 4 2](BF4)2 7, [ClO4 - ⊂ Ag3 L 4 2](ClO4)2 8, and [CuI3 2- ⊂ Cu3 L 4 2]2[Cu2I4] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L 1 ligands are connected by two linearly coordinated Ag+ ions. 2 and 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag+ ions and two L 2 or L 3 ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag+ ions in trigonal planar coordination linked by three L 3 ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu2+ or Ni2+ ions linked by four L 2 ligands. The topologies of 7−9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag+ or Cu+ ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. 1H NMR and ESI-MS were utilized to elucidate the solution structures of these macrocycles.
AbstractList Three angular ditopic ligands (1,3-bis(benzimidazol-1 -ylmethyl)-4,6-dimethylbenzene L-1, 1,3-bis (benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L-2, and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L-3) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L-4 have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures: [Ag2L21(BF4)(2) 1, [Ag2L22](CF3SO3)(2) 2, [CF3SO3- subset of Ag2L23]-CF3SO3 3, [CF3SO3- subset of Ag2L33]CF3SO3 4, [ClO4- subset of Cu2L42](Clo(4))(3) 5, [4H(2)O subset of (Ni2L4Cl4)-Cl-2].6H(2)O 6, [EF4- subset of Ag3L24](BF4)(2) 7, [ClO4- subset of Ag3L24](ClO4)(2) 8, and [Cul(3)(2-) subset of Cu3L24](2)[Cu2I4] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L-1 ligands are connected by two linearly coordinated Ag+ ions. 2 and 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag+ ions and two L-2 or L-3 ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag+ ions in trigonal planar coordination linked by three L3 ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu2+ or Ni2+ ions linked by four L-2 ligands. The topologies of 7-9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag+ or Cu+ ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. H-1 NMR and ESI-MS were utilized to elucidate the solution structures of these macrocycles.
Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L 1 , 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 2 , and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L 3 ) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 4 have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures:  [Ag2 L 1 2](BF4)2 1, [Ag2 L 2 2](CF3SO3)2 2, [CF3SO3 - ⊂ Ag2 L 3 2]CF3SO3 3, [CF3SO3 - ⊂ Ag2 L 3 3]CF3SO3 4, [ClO4 - ⊂ Cu2 L 2 4](ClO4)3 5, [4H2O ⊂ Ni2 L 2 4Cl4]·6H2O 6, [BF4 - ⊂ Ag3 L 4 2](BF4)2 7, [ClO4 - ⊂ Ag3 L 4 2](ClO4)2 8, and [CuI3 2- ⊂ Cu3 L 4 2]2[Cu2I4] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L 1 ligands are connected by two linearly coordinated Ag+ ions. 2 and 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag+ ions and two L 2 or L 3 ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag+ ions in trigonal planar coordination linked by three L 3 ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu2+ or Ni2+ ions linked by four L 2 ligands. The topologies of 7−9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag+ or Cu+ ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. 1H NMR and ESI-MS were utilized to elucidate the solution structures of these macrocycles.
Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L(1), 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(2), and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L(3)) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(4) have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures: [Ag(2)L(1)(2)](BF(4))(2) 1, [Ag(2)L(2)(2)](CF(3)SO(3))(2) 2, [CF(3)SO(3)(-) subset Ag(2)L(3)(2)]CF(3)SO(3) 3, [CF(3)SO(3)(-) subset Ag(2)L(3)(3)]CF(3)SO(3) 4, [ClO(4)(-) subset Cu(2)L(2)(4)](ClO(4))(3) 5, [4H(2)O subset Ni(2)L(2)(4)Cl(4)].6H(2)O 6, [BF(4)(-) subset Ag(3)L(4)(2)](BF(4))(2) 7, [ClO(4)(-) subset Ag(3)L(4)(2)](ClO(4))(2) 8, and [CuI(3)(2-) subset Cu(3)L(4)(2)](2)[Cu(2)I(4)] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L(1) ligands are connected by two linearly coordinated Ag(+) ions. 2 and 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag(+) ions and two L(2) or L(3) ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag(+) ions in trigonal planar coordination linked by three L(3) ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu(2+) or Ni(2+) ions linked by four L(2) ligands. The topologies of 7-9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag(+) or Cu(+) ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. (1)H NMR and ESI-MS were utilized to elucidate the solution structures of these macrocycles.
Author zur Loye, Hans-Conrad
Cai, Yue-Peng
Su, Cheng-Yong
Chen, Chun-Long
Smith, Mark D
Kaim, Wolfgang
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  givenname: Cheng-Yong
  surname: Su
  fullname: Su, Cheng-Yong
– sequence: 2
  givenname: Yue-Peng
  surname: Cai
  fullname: Cai, Yue-Peng
– sequence: 3
  givenname: Chun-Long
  surname: Chen
  fullname: Chen, Chun-Long
– sequence: 4
  givenname: Mark D
  surname: Smith
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– sequence: 5
  givenname: Wolfgang
  surname: Kaim
  fullname: Kaim, Wolfgang
– sequence: 6
  givenname: Hans-Conrad
  surname: zur Loye
  fullname: zur Loye, Hans-Conrad
BackLink http://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=14980002$$DView record in Pascal Francis
https://www.ncbi.nlm.nih.gov/pubmed/12848568$$D View this record in MEDLINE/PubMed
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Keywords CYCLIC NANOSTRUCTURES
COPPER(II) COMPLEXES
CAGE-LIKE COMPLEX
NANOPOROUS NETWORK
TRIPLE-STRANDED HELICATE
SILVER(I) COMPLEXES
COORDINATION POLYMERS
ELECTROSPRAY MASS-SPECTROMETRY
SOLID-STATE
RATIONAL DESIGN
Cationic complex
Molecular packing
Nickel Complexes
Silver Complexes
Trinuclear complex
Organic ligand
NMR spectrometry
Inorganic synthesis
Transition metal Complexes
Copper Complexes
X ray diffraction
Molecular assembly
Supramolecular structure
Dinuclear complex
Polynuclear complex
Mass spectrometry
Halo complex
Crystalline structure
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SSID ssj0004281
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Snippet Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L 1 , 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 2 , and...
Three angular ditopic ligands (1,3-bis(benzimidazol-1 -ylmethyl)-4,6-dimethylbenzene L-1, 1,3-bis (benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L-2, and...
Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L(1), 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(2), and...
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SubjectTerms Chemistry
Chemistry, Multidisciplinary
Condensed matter: structure, mechanical and thermal properties
Coordination compounds
Exact sciences and technology
Inorganic chemistry and origins of life
Inorganic compounds
Metal complexes
Physical Sciences
Physics
Preparations and properties
Science & Technology
Structure of solids and liquids; crystallography
Structure of specific crystalline solids
Title Ligand-Directed Molecular Architectures:  Self-Assembly of Two-Dimensional Rectangular Metallacycles and Three-Dimensional Trigonal or Tetragonal Prisms
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