Reactions in Solid‐State Inclusion Compounds

This chapter focuses on chemical reactions occurring within solid organic inclusion compounds, encompassing a broad range of inclusion compounds and a wide variety of different reaction types, including reactions of the guest molecules (such as dimerization, polymerization, cyclization, isomerization, and decomposition), reactions involving the host molecules, and guest exchange processes. In many cases, chemical transformations of guest molecules confined within solid host structures proceed with a high degree of selectivity toward a single product, and often with a high degree of stereoselectivity and/or enantioselectivity, as a consequence of the geometrical constraints imposed on the reacting molecules by the host structure. For this reason, the products obtained from such reactions are often significantly different from those obtained from the corresponding reactions in the solution state or in the “pure” crystalline phase of the guest molecules. Through the examples highlighted in this chapter, general issues relating to reactions in solid organic inclusion compounds are rationalized and discussed.

[1]  F. Cataldo,et al.  Asymmetric radiation-induced inclusion polymerization of 3-methyl-1,4-pentadiene in deoxycholic acid , 2010 .

[2]  F. Cataldo,et al.  Inclusion polymerization of isoprene in deoxycholic acid , 2009 .

[3]  F. Cataldo,et al.  Radiation-induced polymerization of 2,3-dimethyl-1,3-butadiene clathrate in deoxycholic acid , 2009 .

[4]  K. Harris,et al.  Bidirectional Transport of Guest Molecules through the Nanoporous Tunnel Structure of a Solid Inclusion Compound , 2009 .

[5]  F. Cataldo,et al.  Synthesis of highly crystalline poly(dimethylbutadiene) (PDMB) by radiation-induced inclusion polymerization: A comparison with PDMBs synthesized by bulk and emulsion polymerization , 2008 .

[6]  J. Howard,et al.  Controlled photochemical reaction of 4-oxo(phenylacetyl)morpholine and 1-(phenylglyoxylyl)piperidine in solid supramolecular systems , 2008 .

[7]  Christophe M. L. Vande Velde,et al.  Competitive isomerization and dimerization in co-crystals of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol and sorbic acid: a new look at stereochemical requirements for [2+2] dimerization. , 2008, Chemical communications.

[8]  A. Tonelli,et al.  Why is Stereoregular Polyacrylonitrile Obtained by Polymerization in Urea Canals Isotactic , 2007 .

[9]  K. Harris,et al.  Kinetics of molecular transport in a nanoporous crystal studied by confocal Raman microspectrometry: single-file diffusion in a densely filled tunnel. , 2007, The journal of physical chemistry. B.

[10]  Philip Coppens,et al.  Single-crystal-to-single-crystal E-->Z and Z-->E isomerizations of 3-chloroacrylic acid within the nanocavities of a supramolecular framework. , 2007, Chemical Communications.

[11]  Ayesha Jacobs,et al.  Inclusion by a Xanthenol Host: Relating Structure to the Kinetics of Desolvation and Guest Exchange , 2007 .

[12]  K. Harris Fundamental and Applied Aspects of Urea and Thiourea Inclusion Compounds , 2007 .

[13]  K. Harris,et al.  Significant conformational changes associated with molecular transport in a crystalline solid. , 2006, The journal of physical chemistry. B.

[14]  Jingxia Wang,et al.  Highly regio- and enantioselective thermal [2 + 2] cycloaddition of coumarin in a crystalline inclusion complex under high vacuum. , 2005, Chemical communications.

[15]  T. Maris,et al.  Molecular tectonics. Selective exchange of cations in porous anionic hydrogen-bonded networks built from derivatives of tetraphenylborate. , 2005, Journal of the American Chemical Society.

[16]  S. Hirano,et al.  New [4 + 4] photodimerization of 5-chloro-2-pyridone to the meso-cis-syn dimmer as an inclusion complex with 1,2,4,5-benzenetetracarboxylic acid , 2004 .

[17]  Yana Sheynin,et al.  The Effects of Space Formed by Host Molecules in Inclusion Compounds on the Homogeneity/Heterogeneity of the Photoreaction in the Solid State , 2004 .

[18]  K. Harris,et al.  Direct time-resolved and spatially resolved monitoring of molecular transport in a crystalline nanochannel system. , 2004, Journal of the American Chemical Society.

[19]  Kazuaki Kato,et al.  Drastic Increase in the Flexibility of Open Host Frameworks of a Steroidal Host Compound upon Shortening Its Spacer , 2004 .

[20]  G. Kaupp,et al.  Unidirectional cis-trans photoisomerization of cis-3,3′-bis(diphenylhydroxymethyl)stilbene in inclusion complex crystals , 2003 .

[21]  T. Maris,et al.  Deformation of porous molecular networks induced by the exchange of guests in single crystals. , 2003, Journal of the American Chemical Society.

[22]  K. Harris,et al.  Design of a solid inclusion compound with optimal properties as a linear dichroic filter for X-ray polarization analysis. , 2003, Angewandte Chemie.

[23]  K. Sada,et al.  Inclusion Polymerization in Polymorphic Crystals of Cholic Acid , 2001 .

[24]  I. Miyahara,et al.  Single-Crystal-to-Single-Crystal Enantioselective [2+2] Photodimerization of Coumarin, Thiocoumarin and Cyclohex-2-enone in the Inclusion Complexes with Chiral Host Compounds , 2000 .

[25]  F. Guillaume Des cristaux organiques d'intercroissance incommensurables 1-D : les composés d'inclusion de l'urée , 1999 .

[26]  K. Harris,et al.  The design of a molecularly selective capillary based on an incommensurate intergrowth structure , 1999 .

[27]  Yukiko Takahashi,et al.  Enantioselective Photocyclization of N-Alkylfuran-2-carboxyanilides to trans-Dihydrofuran Derivatives in Inclusion Crystals with Optically Active Host Compounds Derived from Tartaric Acid. , 1999, The Journal of organic chemistry.

[28]  M. White,et al.  Destruction of the urea host lattice by the photochemical fragmentation of molecular guests , 1998 .

[29]  K. Harris Meldola Lecture: understanding the properties of urea and thiourea inclusion compounds , 1998 .

[30]  R. Kuroda,et al.  Enantioselective Photocyclization of 2-Arylthio-3-methylcyclohexen-1-ones to Dihydrobenzothiophene Derivatives in an Inclusion Crystal with an Optically Active Host , 1996 .

[31]  F. Toda,et al.  1:1 and 2:1 Inclusion Complexes of (R,R)-(-)-trans-2,3-Bis(hydroxydiphenyl- methyl)-1,4-dioxaspiro[4.4]nonane with N-Allylfuran-2-carboxanilide Which upon Irradiation in the Solid State Give (-)- and (+)-Photocyclization Products, Respectively. , 1996, The Journal of organic chemistry.

[32]  K. Harris,et al.  Superspace group descriptions of the symmetries of incommensurate urea inclusion compounds , 1996, Proceedings of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[33]  K. Harris Structural and dynamic properties of urea and thiourea inclusion compounds , 1996 .

[34]  J. Trotter,et al.  Modification of host photobehavior by formation of crystalline host-guest assemblies , 1995 .

[35]  A. Sekiya,et al.  Topological and Nontopological Rearrangement in Crystal-Lattice of Cholic-Acid Inclusion Complex-Induced by Guest Exchange , 1995 .

[36]  H. Allcock,et al.  Inclusion polymerization within a tris(2,3-naphthylenedioxy)cyclotriphosphazene clathrate , 1994 .

[37]  H. Allcock,et al.  Stereocontrolled Polymerization within a Cyclophosphazene Clathrate Tunnel System , 1994 .

[38]  Keiji Kobayashi,et al.  Solid-State Photosolvolysis of Clathrate Crystals Including Ethanol as a Guest Component , 1994 .

[39]  K. Ute,et al.  Determination of Stereoregularity of .gamma.-Irradiation Canal Polymerized Polyacrylonitrile by 1H 2D J-Resolved NMR Spectroscopy , 1994 .

[40]  K. Harris Investigating the Structure and Dynamics of a Family of Organic Solids: The Alkane/Urea Inclusion Compounds , 1993 .

[41]  R. Weiss,et al.  Photodimerization of coumarins in solid cyclodextrin inclusion complexes , 1992 .

[42]  J. Thomas Solid Acid Catalysts , 1992 .

[43]  Koichi Tanaka,et al.  Selective photodimerisations of coumarin in crystalline inclusion compounds , 1992 .

[44]  J. N. Moorthy,et al.  Stereospecific photodimerization of coumarins in crystalline inclusion complexes. Molecular and crystal structure of 1:2 complex of (S,S)-(-)-1,6-bis(o-chlorophenyl)-1,6-diphenyl-hexa-2,4-diyne-1,6-diol and coumarin , 1991 .

[45]  J. McBride,et al.  Photochemical Mechanism in Single Crystals: FTIR Studies of Diacyl Peroxides , 1991 .

[46]  N. Kasai,et al.  Guest-responsive structural changes in cholic acid intercalation crystals , 1990, Nature.

[47]  K. Harris,et al.  Structural aspects of urea inclusion compounds and their investigation by X-ray diffraction: a general discussion , 1990 .

[48]  K. Harris,et al.  Structural aspects of the chlorocyclohexane/thiourea inclusion system , 1990 .

[49]  B. E. Robertson,et al.  Adamantane inclusion complexes with thiourea and selenourea , 1989 .

[50]  F. Lewis,et al.  Lewis acid catalysis of photochemical reactions. 8. Photodimerization and cross-cycloaddition of coumarin , 1989 .

[51]  N. Kasai,et al.  New channel type inclusion compound of steroidal bile acid. Structure of 1:1 complex between cholic acid and acetophenone , 1988 .

[52]  M. Kaftory Reactions in the solid state. III: Structural aspects of photochemical reactions in crystalline inclusion compounds , 1987 .

[53]  R. Gerdil Tri-o-Thymotide Clathrates , 1987 .

[54]  K. Harris,et al.  ESR and X-ray diffraction studies of diacyl peroxides in urea and aluminosilicate hosts , 1987 .

[55]  M. Sakamoto,et al.  Solid state photoreaction of n,n-dialkylpyruvamides: inclusion complexes with deoxycholic acid or cyclodextrin , 1987 .

[56]  R. Popovitz‐Biro,et al.  Elucidation of reaction pathways in host-guest complexes by crystal engineering. Photoaddition of carbonyl group of guest acetophenones and propiopheno , 1987 .

[57]  Alessio Guarino,et al.  Phototransformations in nonhomogeneous media: cis-trans-isomerization of olefins in inclusion compounds , 1987 .

[58]  Bruce A. Weber,et al.  Mechanical Stress and Reactivity in Organic Solids , 1986, Science.

[59]  N. Turro,et al.  Modification of chemical reactivity via inclusion complex formation: photochemistry of dibenzyl ketones and benzyl phenylacetates , 1986 .

[60]  M. Hasegawa Topochemical photopolymerization of diolefin crystals , 1986 .

[61]  H. Allcock,et al.  Stereocontrolled polymerization of acrylic monomers within a tris(o-phenylenedioxy)cyclotriphosphazene tunnel clathrate , 1985 .

[62]  R. Popovitz‐Biro,et al.  Reaction pathways in crystalline host-guest inclusion complexes: rotation by a net 180.degree. of the acetyl group on photoaddition of guest acetophenone and m-chloroacetophenone to the atom C5 of host deoxycholic acid , 1985 .

[63]  R. Popovitz‐Biro,et al.  SOLID-STATE PHOTOCHEMISTRY OF GUEST ALIPHATIC KETONES INSIDE THE CHANNELS OF HOST DEOXYCHOLIC AND APOCHOLIC ACIDS , 1985 .

[64]  L. Zetta,et al.  Inclusion asymmetric polymerization in deoxycholic acid by "through-space" asymmetric induction , 1984 .

[65]  J. Scaiano,et al.  Photodecomposition of alkanones in urea inclusion compounds , 1983 .

[66]  H. Allcock,et al.  Polymerization in clathrate tunnel systems: stereocontrolled polymerization of unsaturated monomers in crystals of tris(o-phenylenedioxy)cyclotriphosphazene , 1982 .

[67]  P. Sozzani,et al.  Optically active block copolymers by inclusion polymerization: Evidence for ‘through-space’ asymmetric induction , 1981 .

[68]  R. Arad-Yellin,et al.  Cis-trans photoisomerization in a tri-o-thymotide clathrate. Crystal structure of tri-o-thymotide clathrates of cis- and trans-stilbene , 1979 .

[69]  J. M. Thomas,et al.  Organic reactions in the solid state: accident and design , 1979 .

[70]  R. Popovitz‐Biro,et al.  REACTIONS IN INCLUSION MOLECULAR COMPLEXES. 2. A TOPOCHEMICAL SOLID-STATE PHOTOADDITION OF ACETONE TO DEOXYCHOLIC ACID , 1978 .

[71]  E. Hough,et al.  X-Ray crystallographic studies on ferrocene included in a thiourea host lattice , 1978 .

[72]  G. Audisio,et al.  Inclusion asymmetric polymerization of penta-1,3-dienes in deoxycholic acid , 1976 .

[73]  M. Cohen The Photochemistry of Organic Solids , 1975 .

[74]  M. Miyata,et al.  Radiation-induced polymerization of 2,3-disubstituted butadienes in deoxycholic acid inclusion compounds , 1975 .

[75]  R. Popovitz‐Biro,et al.  Reactions in inclusion molecular complexes. A one-step regiospecific and stereospecific hydroxylation of deoxycholic acid , 1975 .

[76]  Y. Chatani,et al.  Structural Investigation of Radiation-Induced Urea Canal Polymerization of 1,3-Butadiene , 1975 .

[77]  John Meurig Thomas Topography and topology in solid-state chemistry , 1974, Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences.

[78]  M. Iwasaki,et al.  ESR Studies on Radiation-Induced Polymerization of 1,3-Butadiene in Urea Canal Complexes , 1973 .

[79]  Y. Chatani,et al.  Structural Evidence of Radiation-Induced Thiourea Canal Polymerization of 2,3-Disubstituted 1,3-Butadienes , 1972 .

[80]  M. Gramegna,et al.  Stereospecific and Asymmetric Inclusion Polymerization. III. Polymerization of Substituted Butadienes Included in Racemic Perhydrotriphenylene , 1972 .

[81]  G. Allegra,et al.  Single Crystal to Single Crystal Transformation of Perhydrotriphenylene Inclusion Compounds during Canal Polymerization of Butadiene , 1971 .

[82]  Gerhard M. J. Schmidt,et al.  Photodimerization in the solid state , 1971 .

[83]  H. Tadokoro,et al.  Structural Study of the Polymerization of 2,3-Dichlorobutadiene in the Thiourea Canal Complex. Structural Change during Canal Polymerization and the Crystal Structure of the Resultant Polymer , 1970 .

[84]  M. Gramegna,et al.  Stereospecific and Asymmetric Inclusion Polymerization I. Polymerization of trans- and cis-1,3-Pentadiene Included in Racemic Perhydrotriphenylene , 1970 .

[85]  G. Natta,et al.  Inclusion compounds of linear polymers and polymerization of monomers included in perhydrotriphenylene , 1967 .

[86]  G. Audisio,et al.  Asymmetric synthesis. Radiation polymerization of trans-1,3-pentadiene included in optically active perhydrotriphenylene , 1967 .

[87]  M. Cohen Photochemistry of the organic solid state , 1964 .

[88]  M. D. Cohen,et al.  383. Topochemistry. Part I. A survey , 1964 .

[89]  D. White Stereospecific Polymerization in Urea Canal Complexes1 , 1960 .

[90]  H. Lenné Röntgenographische Strukturuntersuchungen hexagonaler Einschlussverbindungen des Thioharnstoffs , 1954 .

[91]  A. Smith The crystal structure of the urea–hydrocarbon complexes , 1952 .

[92]  V. Kohlschütter,et al.  Zur Kenntnis topochemischer Reaktionen. Über Bildung und Verhalten von Kupferhydroxyd , 1920 .