Reactivity of self-assembled supramolecular complexes in the gas phase: A supramolecular neighbor group effect

Abstract Infrared multi-photon dissociation (IRMPD) spectra of mass-selected, self-assembled supramolecular squares and their gas-phase fragments have been recorded in a Fourier-transform ion-cyclotron resonance (FT-ICR) mass spectrometer. The squares have been transferred into the gas phase by electrospray ionization (ESI) under very soft ionization conditions resulting in a series of signals for intact squares in different charge states by stripping off two or more counter ions. The fragmentation patterns of the squares strongly depend on the parent ion's charge state. For species with a lower number of charges, expulsions of edge ligands prevail, whereas charge separation pathways dominate the dissociation pathways of more highly charged species.

[1]  M. Maestro,et al.  Equilibria between metallosupramolecular squares and triangles with the new rigid linker 1,4-bis(4-pyridyl)tetrafluorobenzene. Experimental and theoretical study of the structural dependence of NMR data. , 2003, Inorganic chemistry.

[2]  F. Würthner,et al.  Fluorescent and electroactive cyclic assemblies from perylene tetracarboxylic acid bisimide ligands and metal phosphane triflates. , 2001, Chemistry.

[3]  G. Swiegers,et al.  Multiple-Interaction Self-Assembly in Coordination Chemistry , 2001 .

[4]  K. Biradha,et al.  Pd(II)- and Pt(II)-Linked Tetranuclear Complexes as Assembly Units for Higher Ordered Structures. , 1999 .

[5]  M. Fujita,et al.  Metal-directed self-assembly of two- and three-dimensional synthetic receptors , 1998 .

[6]  M. Albrecht.  Dicatechol ligands: novel building-blocks for metallo-supramolecular chemistry , 1998 .

[7]  M. Fujita,et al.  Preparation of a macrocyclic polynuclear complex, [(en)Pd(4,4'-bpy)]4(NO3)8 (en = ethylenediamine, bpy = bipyridine), which recognizes an organic molecule in aqueous media , 1990 .

[8]  Chad A. Mirkin,et al.  Strategies for the Construction of Supramolecular Compounds through Coordination Chemistry. , 2001, Angewandte Chemie.

[9]  R. Ziessel,et al.  Monitoring the iron(II)-induced self-assembly of preorganized tritopic ligands by electrospray mass spectrometry: unique formation of metallomacrocycles , 1996 .

[10]  C. Lebrilla.  The gas-phase chemistry of cyclodextrin inclusion complexes. , 2001, Accounts of chemical research.

[11]  P. Stang,et al.  MIXED, NEUTRAL-CHARGED, PLATINUM-PLATINUM AND PLATINUM-PALLADIUM MACROCYCLIC TETRANUCLEAR COMPLEXES , 1994 .

[12]  M. Albrecht,et al.  "Let's twist again"--double-stranded, triple-stranded, and circular helicates. , 2001, Chemical reviews.

[13]  E. Freisinger,et al.  Anion pore structure through packing of molecular triangles , 1999 .

[14]  C. Schalley,et al.  Mass spectrometric characterization and gas-phase chemistry of self-assembling supramolecular squares and triangles. , 2002, Chemistry.

[15]  F. Würthner,et al.  A triangle-square equilibrium of metallosupramolecular assemblies based on pd(II) and pt(II) corners and diazadibenzoperylene bridging ligands. , 2001, Journal of the American Chemical Society.

[16]  M. Glocker,et al.  Electrospray Mass Spectrometry of Biomacromolecular Complexes with Noncovalent Interactions—New Analytical Perspectives for Supramolecular Chemistry and Molecular Recognition Processes , 1996 .

[17]  C. Schalley.  Molecular recognition and supramolecular chemistry in the gas phase. , 2001, Mass spectrometry reviews.

[18]  P. Stang,et al.  Design and Study of Synthetic Chiral Nanoscopic Assemblies. Preparation and Characterization of Optically Active Hybrid, Iodonium−Transition-Metal and All-Transition-Metal Macrocyclic Molecular Squares , 1996 .

[19]  Laura Rodríguez,et al.  Study of the self-assembly reactions between the organic linker 1,4-bis(4-pyridyl)butadiyne and the metal-containing corners (diphosphine)M(II) (M=Pd, Pt; diphosphine=dppp, dppf, depe, dppbz) , 2003 .

[20]  Jean-Marie Lehn,et al.  Comprehensive Supramolecular Chemistry , 1996 .

[21]  A. Lees,et al.  New Self-Assembly Luminescent Molecular Triangle and Square Rhenium(I) Complexes , 1999 .

[22]  H. Yun,et al.  GUEST-INDUCED REORGANIZATION OF A SELF-ASSEMBLED PD(II) COMPLEX , 1998 .

[23]  C. Schalley.  Supramolecular chemistry goes gas phase: the mass spectrometric examination of noncovalent interactions in host–guest chemistry and molecular recognition , 2000 .

[24]  K. Severin,et al.  Chemisch schaltbare Selbstorganisation von chiralen dreieckigen Metallamakrocyclen , 1999 .

[25]  E. Zangrando,et al.  MOLECULAR TRIANGLE FROM ENPTII AND 2,2'-BIPYRAZINE , 1998 .

[26]  C. Piguet.  Helicates and Related Metallosupramolecular Assemblies: Toward Structurally Controlled and Functional Devices , 1999 .

[27]  Shie-Ming Peng,et al.  Gezielte Selbstorganisation von Makrocyclen mit drei Metallzentren und Benzimidazol als nichtlinearem Brückenglied: Kristallstruktur eines lumineszierenden Platin(II)‐Cyclotrimers , 1999 .

[28]  M. Fujita,et al.  Supramolecular Self-Assembly of Macrocycles, Catenanes, and Cages through Coordination of Pyridine-Based Ligands to Transition Metals , 1996 .

[29]  J. Hupp,et al.  Self-Assembly of Luminescent Molecular Squares Featuring Octahedral Rhenium Corners. , 1996, Inorganic chemistry.

[30]  P. Stang,et al.  FAST ATOM BOMBARDMENT MASS SPECTROMETRY FOR CHARACTERIZING CATIONIC CHELATED SPECIES , 1996 .

[31]  P. Stang,et al.  Transition Metal Based Cationic Molecular Boxes. Self-Assembly of Macrocyclic Platinum(II) and Palladium(II) Tetranuclear Complexes , 1994 .

[32]  Douglas Philp,et al.  Self‐Assembly in Natural and Unnatural Systems , 1996 .

[33]  Woessner Sm,et al.  Luminescent Squares and Rings Based on Metal-to-Ligand Charge Transfer Excited States. , 1999 .

[34]  A. Lees,et al.  Self-Assembly Triangular and Square Rhenium(I) Tricarbonyl Complexes: A Comprehensive Study of Their Preparation, Electrochemistry, Photophysics, Photochemistry, and Host−Guest Properties , 2000 .

[35]  J. Leary,et al.  Electrospray ionization ion trap mass spectrometry of a tetrahedral supramolecular Ti4L4 cluster , 1998 .

[36]  J. Henion,et al.  Ion spray-tandem mass spectrometry of supramolecular coordination complexes , 1994, Journal of the American Society for Mass Spectrometry.

[37]  E. Freisinger,et al.  Molecular Architecture Based on Metal Triangles Derived from 2,2‘-Bipyrazine (Bpz) and EnMII (M = Pt, Pd) , 2000 .

[38]  G. Whitesides,et al.  Molecular self-assembly and nanochemistry: a chemical strategy for the synthesis of nanostructures. , 1991, Science.

[39]  M. Przybylski,et al.  Elektrospray‐Massenspektrometrie von Biomakromoleülkomplexen mit nichtkovalenten Wechselwirkungen – neue analytische Perspektiven für supramolekulare Chemie und molekulare Erkennungsprozesse , 1996 .

[40]  P. Stang,et al.  Self-Assembly of Cationic, Tetranuclear, Pt(II) and Pd(II) Macrocyclic Squares. x-ray Crystal Structure of [Pt2+(dppp)(4,4'-bipyridyl).cntdot.2-OSO2CF3]4 , 1995 .

[41]  Gérald Bernardinelli,et al.  Helicates as Versatile Supramolecular Complexes. , 1997, Chemical reviews.

[42]  F. Cotton,et al.  Supramolecular arrays based on dimetal building units. , 2001, Accounts of chemical research.

[43]  C. Che,et al.  Self-Assembly of Predesigned Trimetallic Macrocycles Based on Benzimidazole as Nonlinear Bridging Motifs: Crystal Structure of a Luminescent Platinum(II) Cyclic Trimer. , 1999, Angewandte Chemie.

[44]  Richard D. Smith,et al.  Molecular Architecture via Coordination: Marriage of Crown Ethers and Calixarenes with Molecular Squares, Unique Tetranuclear Metallamacrocycles from Metallacrown Ether and Metallacalixarene Complexes via Self-Assembly , 1997 .

[45]  Christoph A. Schalley,et al.  Template zweiter Ordnung: geordnete Schichten aus supramolekularen Quadraten auf einer Chlorid‐bedeckten Cu(100)‐Oberfläche , 2004 .

[46]  Katsuyuki Ogura,et al.  Transition-metal-directed assembly of well-defined organic architectures possessing large voids: From macrocycles to [2] catenanes , 1996 .

[47]  M. Albrecht,et al.  Approaching supramolecular functionality. , 2004, Chemistry.

[48]  Kimoon Kim,et al.  Characterization of Self-Assembling Nano-Sized Structures by Means of Coldspray Ionization Mass Spectrometry , 2000 .

[49]  J. Lehn,et al.  Electrospray mass spectrometry of the self-assembly of a capped polymetallic complex , 1993 .

[50]  F. Würthner,et al.  Highly fluorescent and electroactive molecular squares containing perylene bisimide ligands , 2000 .

[51]  Jeffery A. Whiteford,et al.  FAST-ATOM-BOMBARDMENT-MASSENSPEKTROMETRIE ZUR CHARAKTERISIERUNG KATIONISCHER CHELATE , 1996 .

[52]  A. van Dorsselaer,et al.  Self-Assembly of an 11-Component Cylindrical Inorganic Architecture: Electrospray Mass Spectrometry and Thermodynamic Studies. , 1996, Inorganic chemistry.

[53]  P. Stang,et al.  Self-assembly of discrete cyclic nanostructures mediated by transition metals. , 2000, Chemical reviews.

[54]  T. Mitsuhashi,et al.  On the structure of transition-metal-linked molecular squares , 1996 .

[55]  J. Brodbelt.  Probing molecular recognition by mass spectrometry , 2000 .

[56]  J. Hupp,et al.  Luminescent Rhenium/Palladium Square Complex Exhibiting Excited State Intramolecular Electron Transfer Reactivity and Molecular Anion Sensing Characteristics , 1995 .

[57]  J. Lehn,et al.  Investigation of the Self‐Assembly Pathway of Pentanuclear Helicates by Electrospray Mass Spectrometry , 1996 .

[58]  C. Piguet,et al.  Characterization of supramolecular complexes by high resolution electrospray ionization mass spectrometry , 1999 .

[59]  B. Kirchner,et al.  Synthesis of chiral self-assembling rhombs and their characterization in solution, in the gas phase, and at the liquid-solid interface. , 2005, Journal of the American Chemical Society.

[60]  M. Fujita,et al.  Macrocyclic dinuclear complexes self-assembled from (en)Pd(NO3)2 and pyridine-based bridging ligands , 1996 .

[61]  B. Lippert,et al.  MOLEKULARES DREIECK AUS ENPTII UND 2,2'-BIPYRAZIN , 1998 .

[62]  Severin,et al.  Chemically Triggered Assembly of Chiral Triangular Metallomacrocycles. , 1999, Angewandte Chemie.

[63]  Chad A. Mirkin,et al.  Koordinationschemische Synthesemethoden zum Aufbau supramolekularer Verbindungen , 2001 .

[64]  G. Ercolani.  Physical Basis of Self-Assembly Macrocyclizations , 1998 .

[65]  Douglas Philp,et al.  SELBSTORGANISATION IN NATURLICHEN UND IN NICHTNATURLICHEN SYSTEMEN , 1996 .

[66]  C. Schalley,et al.  Second-order templation: ordered deposition of supramolecular squares on a chloride-covered Cu(100) surface. , 2004, Angewandte Chemie.

[67]  Kenneth N. Raymond,et al.  Supermolecules by Design , 1999 .

[68]  C. Hunter,et al.  Self-assembly of macrocyclic porphyrin oligomers , 1995 .

[69]  J. Leary,et al.  Combinatorial Libraries of Metal–Ligand Assemblies with an Encapsulated Guest Molecule , 2001 .

[70]  Richard D. Smith,et al.  Nanoscale Tectonics: Self-Assembly, Characterization, and Chemistry of a Novel Class of Organoplatinum Square Macrocycles , 1997 .

[71]  Kumar Biradha,et al.  Molecular paneling via coordination , 2001 .

[72]  M. Vincenti.  Special feature: Perspective. Host–guest chemistry in the mass spectrometer , 1995 .

[73]  J. Hupp,et al.  Synthesis, Characterization, and Preliminary Host-Guest Binding Studies of Porphyrinic Molecular Squares Featuring fac-Tricarbonylrhenium(I) Chloro Corners , 1997 .

[74]  P. Stang,et al.  Self-Assembly, Symmetry, and Molecular Architecture: Coordination as the Motif in the Rational Design of Supramolecular Metallacyclic Polygons and Polyhedra , 1997 .

[75]  Jonathan S. Lindsey,et al.  Self-Assembly in Synthetic Routes to Molecular Devices. Biological Principles and Chemical Perspectives: A Review , 1991 .

[76]  M. Licchelli,et al.  Fluorescence Redox Switching Systems Operating through Metal Centres: the NiIII/NiII Couple , 1996 .