Leonard R. MacGillivray

Supramolecular Construction of an Aldehyde–Cyclobutane via the Solid State: Combining Reversible Imine Formation and Metal–Organic Self-Assembly

Co-reporter:Shalisa M. Oburn, Dale C. Swenson, S. V. Santhana Mariappan, and Leonard R. MacGillivray

Journal of the American Chemical Society June 28, 2017 Volume 139(Issue 25) pp:8452-8452

Publication Date(Web):June 12, 2017

DOI:10.1021/jacs.7b04420

A combination of metal–organic self-assembly and reversible imine formation is used to achieve an organic synthesis via the solid state. Imine bond formation is employed to install a pyridyl to the alkene trans-cinnamaldehyde while Ag(I) ions are used in a second step to assemble the pyridyl-functionalized alkene into a geometry in the solid state for an intermolecular [2 + 2] photodimerization. The alkene undergoes the cycloaddition reaction via a 1D coordination polymer to generate a pyridyl-functionalized cyclobutane stereoselectively and in quantitative yield. Removal of the pyridyl group affords the aldehyde-functionalized cyclobutane α-truxilaldehyde.

Edge-to-Edge C–H···N Hydrogen Bonds in Two-Component Co-crystals Aide a [2 + 2] Photodimerization

Co-reporter:Cristian M. Santana, Eric W. Reinheimer, Herman R. Krueger Jr., Leonard R. MacGillivray, and Ryan H. Groeneman

Crystal Growth & Design April 5, 2017 Volume 17(Issue 4) pp:2054-2054

Publication Date(Web):March 13, 2017

DOI:10.1021/acs.cgd.7b00040

C–H···N hydrogen bonds support an intermolecular [2 + 2] photodimerization in the solid state. The photocycloaddition occurs in a co-crystal of composition (tbrb)·(4,4′-bpe) (where tbrb = 1,2,4,5-tetrabromobenzene; 4,4′-bpe = trans-1,2-bis(4-pyridyl)ethylene) that consists of one-dimensional (1D) chains that self-assemble to form corrugated sheets. Stacking of 4,4′-bpe between sheets conforms to the topochemical postulate of Schmidt. The alkene reacts to form rctt-tetrakis(4-pyridyl)cyclobutane (4,4′-tpcb) stereoselectively and in quantitative yield. C–H···N hydrogen bonds also support the assembly of the components in (tbrb)·(4,4′-azo) (where: 4,4′-azo = 4,4′-azopyridine) into planar sheets. Density-functional theory calculations reveal identical face-to-face stacks of tbrb to aide in the stabilization of the structures of the co-crystals.

Generation of cocrystals of Tavaborole (AN2690): opportunities for boron-containing APIs

Co-reporter:Gonzalo Campillo-Alvarado;Colton A. Staudt;Melissa J. Bak

CrystEngComm (1999-Present) 2017 vol. 19(Issue 22) pp:2983-2986

Publication Date(Web):2017/06/07

DOI:10.1039/C7CE00314E

Cocrystals of the FDA-approved boron-containing API Tavaborole (AN2690) were obtained through solvent evaporation with coformers functionalized with 4-pyridyl groups. The components form three- and four-component supramolecular assemblies sustained by a combination of (B)OH⋯Npyr hydrogen bonds and C–H⋯F interactions, as demonstrated by single-crystal X-ray diffraction analysis. Three cocrystals are isostructural.

Reducing a cocrystal to nanoscale dimensions enables retention of physical crystal integrity upon dehydration

Co-reporter:Katherine E. Peterson;Rodger F. Henry;Geoff G. Z. Zhang

CrystEngComm (1999-Present) 2017 vol. 19(Issue 27) pp:3723-3726

Publication Date(Web):2017/07/10

DOI:10.1039/C7CE00826K

We report the preparation and dehydration of a cocrystal of caffeine and 2,4-dihydroxybenzoic acid. The dehydration of cocrystals of macro-dimensions results in destruction of crystal morphology; however, crystal morphology is retained when the cocrystal is reduced to nanometer-dimensions, despite a lack of pores to accommodate loss of water.

Stereoselective and quantitative [2 + 2] photodimerization of a symmetrical octafluoro stilbene in the solid state: Face-to-face stacking of the fluorinated rings in trans-1,2-bis(2,3,5,6-tetrafluorophenyl)ethylene

Co-reporter:Michael A. Sinnwell, Benjamin J. Ingenthron, Ryan H. Groeneman, Leonard R. MacGillivray

Journal of Fluorine Chemistry 2016 Volume 188() pp:5-9

Publication Date(Web):August 2016

DOI:10.1016/j.jfluchem.2016.05.010

•Stereoselective and quantitative [2 + 2] photodimerization.•Solid-state synthesis of fluoroarene.•Polyfluorophenyl interactions.The symmetrical octafluoro stilbene trans-1,2-bis(2,3,5,6-tetrafluorophenyl)ethylene (1) undergoes a stereoselective and quantitative [2 + 2] photodimerization in the solid state. The olefin self-assembles via C-H⋯F and face-to-face interactions of the fluorinated phenyl rings into a geometry for a topochemical photodimerization. The crystal structure and stereochemistry of the photoproduct rctt-1,2,3,4-tetrakis(2,3,5,6-tetrafluorophenyl)cyclobutane (2) has been determined.The symmetrical octafluoro stilbene undergoes a stereoselective and quantitative [2 + 2] photodimerization in the solid state. CH⋯F interactions and face-to-face stacking dominate the self-assembly of the alkene in the solid. The resulting cyclobutane possesses four polyfluoro phenyl groups in a rctt-configuration.

Post-application of dry vortex grinding improves the yield of a [2 + 2] photodimerization: Addressing static disorder in a cocrystal

Co-reporter:Elizabeth Elacqua, Katherine A. Kummer, Ryan H. Groeneman, Eric W. Reinheimer, Leonard R. MacGillivray

Journal of Photochemistry and Photobiology A: Chemistry 2016 Volume 331() pp:42-47

Publication Date(Web):1 December 2016

DOI:10.1016/j.jphotochem.2015.12.004

•[2 + 2] photodimerization conducted in cocrystal.•Yield improved via mechanochemistry.•Cocrystal exhibits static disorder of a carbon–carbon double bond.A post-application of dry vortex grinding is used to improve a solid-state photodimerization to near quantitative yield that without grinding does not go to completion. Variable temperature X-ray crystal structure data support the vortex grinding to overcome detrimental effects of static disorder that suppresses the yield of the photoreaction in the solid.

MetalOrganic Coordination versus Hydrogen Bonding: Highly Efficient Templated Photocycloadditions of Trisubstituted Isomeric Olefins in the Solid State

Co-reporter:Dr. Elizabeth Elacqua;Michael A. Sinnwell;Bradley P. Loren;Paul T. Jurgens;Dr. Ryan H. Groeneman;Dr. Eric W. Reinheimer;Dr. Leonard R. MacGillivray

ChemPlusChem 2016 Volume 81( Issue 8) pp:893-898

Publication Date(Web):

DOI:10.1002/cplu.201600261

Abstract

Trisubstituted olefins are reactants in template-directed, solid-state [2+2] photocycloaddition reactions. Whereas hydrogen-bond-based templates afford crystalline assemblies with olefins that are photostable, Ag^I coordination results in carbon–carbon double bonds that react stereoselectively and result in quantitative yield.

Halogen-Bond-Templated [2+2] Photodimerization in the Solid State: Directed Synthesis and Rare Self-Inclusion of a Halogenated Product

Co-reporter:Michael A. Sinnwell ;Dr. Leonard R. MacGillivray

Angewandte Chemie International Edition 2016 Volume 55( Issue 10) pp:3477-3480

Publication Date(Web):

DOI:10.1002/anie.201510912

Abstract

A ditopic halogen-bond acceptor organizes a diiodooctafluorostilbene for a [2+2] photodimerization reaction to take place between two stilbene molecules in the solid state. The resultant cyclobutane product is functionalized with halogen atoms and undergoes self-assembly to form a channel-type host–guest compound that exhibits a very rare form of self-inclusion.

Halogen-Bond-Templated [2+2] Photodimerization in the Solid State: Directed Synthesis and Rare Self-Inclusion of a Halogenated Product

Co-reporter:Michael A. Sinnwell ;Dr. Leonard R. MacGillivray

Angewandte Chemie 2016 Volume 128( Issue 10) pp:3538-3541

Publication Date(Web):

DOI:10.1002/ange.201510912

Abstract

A ditopic halogen-bond acceptor organizes a diiodooctafluorostilbene for a [2+2] photodimerization reaction to take place between two stilbene molecules in the solid state. The resultant cyclobutane product is functionalized with halogen atoms and undergoes self-assembly to form a channel-type host–guest compound that exhibits a very rare form of self-inclusion.

Mechanical Properties of a Series of Macro- and Nanodimensional Organic Cocrystals Correlate with Atomic Polarizability

Co-reporter:Thilini P. Rupasinghe; Kristin M. Hutchins; Bimali S. Bandaranayake; Suman Ghorai; Chandana Karunatilake; Dejan-Krešimir Bučar; Dale C. Swenson; Mark A. Arnold; Leonard R. MacGillivray;Alexei V. Tivanski

Journal of the American Chemical Society 2015 Volume 137(Issue 40) pp:12768-12771

Publication Date(Web):September 25, 2015

DOI:10.1021/jacs.5b07873

A correlation between Young’s modulus, as determined by using nanoindentation atomic force microscopy (AFM), and atomic polarizability is observed for members of a series of cocrystals based on systematic changes to one cocrystal component. Time domain spectroscopy over terahertz frequencies (THz-TDS) is used for the first time to directly measure the polarizability of macro- and nanosized organic solids. Cocrystals of both macro- and nanodimensions with highly polarizable atoms result in softer solids and correspondingly higher polarizabilities.

Achieving dynamic behaviour and thermal expansion in the organic solid state via co-crystallization

Co-reporter:Kristin M. Hutchins, Ryan H. Groeneman, Eric W. Reinheimer, Dale C. Swenson and Leonard R. MacGillivray

Chemical Science 2015 vol. 6(Issue 8) pp:4717-4722

Publication Date(Web):26 May 2015

DOI:10.1039/C5SC00988J

Thermal expansion involves a response of a material to an external stimulus that typically involves an increase in a crystallographic axis (positive thermal expansion (PTE)), although shrinking with applied heat (negative thermal expansion (NTE)) is known in rarer cases. Here, we demonstrate a means to achieve dynamic molecular motion and thermal expansions in organic solids via co-crystallizations. One co-crystal component is known to exhibit dynamic behaviour in the solid state while the second, when varied systematically, affords co-crystals with linear thermal expansion coefficients that range from colossal to nearly zero. Two co-crystals exhibit rare NTE. We expect the approach to guide the design of molecular solids that enable predesigned motion related to thermal expansion processes.

Intramolecular [2 + 2] Photodimerization Achieved in the Solid State via Coordination-Driven Self-Assembly

Co-reporter:Rebecca C. Laird, Michael A. Sinnwell, Nam P. Nguyen, Dale C. Swenson, S. V. Santhana Mariappan, and Leonard R. MacGillivray

Organic Letters 2015 Volume 17(Issue 13) pp:3233-3235

Publication Date(Web):June 16, 2015

DOI:10.1021/acs.orglett.5b00527

An intramolecular [2 + 2] photocycloaddition is achieved in the organic solid state via self-assembly of Ag(I) ions and an endo-ditopic bipyridine. The cations aide to organize carbon–carbon double (C═C) bonds attached to the bipyridine for the cycloaddition reaction. The C═C bonds react regioselectively and quantitatively to afford a photoproduct with edge-sharing four-, five-, and six-membered rings. Our study demonstrates the first use of a metal–organic template to direct an intramolecular [2 + 2] photodimerization in the organic solid state.

Combination of Argentophilic and Perfluorophenyl-Perfluorophenyl Interactions Supports a Head-to-Head [2 + 2] Photodimerization in the Solid State

Co-reporter:Michael A. Sinnwell, Jonas Baltrusaitis, and Leonard R. MacGillivray

Crystal Growth & Design 2015 Volume 15(Issue 2) pp:538

Publication Date(Web):December 23, 2014

DOI:10.1021/cg501571u

Face-to-face perfluorophenyl–perfluorophenyl interactions (C6F5···C6F5) are achieved in a disilver metal–organic complex. The C6F5···C6F5 interactions along with argentophilic forces support trans-pentafluorostilbazole to undergo a head-to-head [2 + 2] photodimerization to form a cyclobutane that sustains a fluorinated two-dimensional metal–organic framework.

Regiocontrol of the [2 + 2] Photodimerization in the Solid State Using Isosteric Resorcinols: Head-to-Tail Cyclobutane Formation via Unexpected Embraced Assemblies

Co-reporter:Devin P. Ericson, Zachary P. Zurfluh-Cunningham, Ryan H. Groeneman, Elizabeth Elacqua, Eric W. Reinheimer, Bruce C. Noll, and Leonard R. MacGillivray

Crystal Growth & Design 2015 Volume 15(Issue 12) pp:5744

Publication Date(Web):October 21, 2015

DOI:10.1021/acs.cgd.5b00939

Regiocontrolled head-to-head and head-to-tail [2 + 2] photodimerizations of (E)-methyl-3-(pyridin-3-yl)prop-2-enoate are achieved in the solid state using 4,6-di-X-res (where X = Cl, Br, I; res = resorcinol) as small-molecule templates. The components in each co-crystal form discrete, three-component supramolecular assemblies sustained by two O–H···N hydrogen bonds. Whereas the head-to-head photoproduct (rctt)-dimethyl-3,4-bis(pyridin-3-yl)cyclobutane-1,2-dicarboxylate forms using 4,6-di-X-res (X = Cl or Br), the head-to-tail regioisomer (rctt)-dimethyl-2,4-bis(pyridin-3-yl)cyclobutane-1,3-dicarboxylate forms using 4,6-di-I-res. The head-to-tail product is generated via unexpected embraced dimeric assemblies. The stereochemistry of the head-to-tail product is confirmed using single-crystal X-ray diffraction.

Nanocrystals of a Metal–Organic Complex Exhibit Remarkably High Conductivity that Increases in a Single-Crystal-to-Single-Crystal Transformation

Co-reporter:Kristin M. Hutchins ; Thilini P. Rupasinghe ; Lindsay R. Ditzler ; Dale C. Swenson ; John R. G. Sander ; Jonas Baltrusaitis ; Alexei V. Tivanski

Journal of the American Chemical Society 2014 Volume 136(Issue 19) pp:6778-6781

Publication Date(Web):April 23, 2014

DOI:10.1021/ja4131774

Ag(I) is used to form a π-stacked metal–organic solid that exhibits remarkably high electrical conductivity. The solid undergoes a single-crystal-to-single-crystal [2+2] photodimerization to generate a 1D coordination polymer with over 40% higher conductivity. The Ag(I) complex represents the first example of an increase in conductivity resulting from a [2+2] photodimerization. Density of states calculations show a higher contribution from Ag(I) ions to the valence band in the photodimerized solid, supporting the increase in conductivity.

Co-Crystals of a Salicylideneaniline: Photochromism Involving Planar Dihedral Angles

Co-reporter:Kristin M. Hutchins, Saikat Dutta, Bradley P. Loren, and Leonard R. MacGillivray

Chemistry of Materials 2014 Volume 26(Issue 10) pp:3042

Publication Date(Web):April 29, 2014

DOI:10.1021/cm500823t

Two act as one: unexpected dimers of catechol direct a solid-state [2+2] photodimerization in a six-component hydrogen-bonded assembly

Co-reporter:Giannis S. Papaefstathiou, Andrew J. E. Duncan and Leonard R. MacGillivray

Chemical Communications 2014 vol. 50(Issue 100) pp:15960-15962

Publication Date(Web):31 Oct 2014

DOI:10.1039/C4CC07747D

We describe hydrogen-bonded dimers of catechol that act collectively as a single template to direct an intermolecular [2+2] photocycloaddition in the solid state. The directed reactivity involves discrete, six-component hydrogen-bonded assemblies and a photoreaction that occurs stereoselectively and in quantitative yield.

Resorcinol-Templated Head-to-Head Photodimerization of a Thiophene in the Solid State and Unusual Edge-to-Face Stacking in a Discrete Hydrogen-Bonded Assembly

Co-reporter:Kristin M. Hutchins, Joseph C. Sumrak, and Leonard R. MacGillivray

Organic Letters 2014 Volume 16(Issue 4) pp:1052-1055

Publication Date(Web):February 5, 2014

DOI:10.1021/ol4035403

A head-to-head photodimerization of a β-substituted thiophene stacked face-to-face in the solid state using a ditopic hydrogen-bond-donor template is reported. The face-to-face stacking is attributed to contributions of intertemplate forces, which contrasts an assembly wherein the same thiophenes stack edge-to-face yet maintain a discrete hydrogen-bonded structure.

Celebrating the International Year of Crystallography

Co-reporter:Leonard R. MacGillivray

CrystEngComm 2014 vol. 16(Issue 41) pp:9581-9581

Publication Date(Web):17 Sep 2014

DOI:10.1039/C4CE90145B

A graphical abstract is available for this content

Structural macrocyclic supramolecular chemistry

Co-reporter:Kari Rissanen, Leonard J. Barbour and Leonard R. MacGillivray

CrystEngComm 2014 vol. 16(Issue 18) pp:3644-3645

Publication Date(Web):31 Mar 2014

DOI:10.1039/C4CE90042A

A graphical abstract is available for this content

Head-to-tail photodimerization of a thiophene in a co-crystal and a rare adipic acid dimer in the presence of a heterosynthon

Co-reporter:Kristin M. Hutchins, Joseph C. Sumrak, Dale C. Swenson and Leonard R. MacGillivray

CrystEngComm 2014 vol. 16(Issue 26) pp:5762-5764

Publication Date(Web):24 Apr 2014

DOI:10.1039/C4CE00481G

A saturated dicarboxylic acid is employed to achieve a photoreactive hydrogen-bonded assembly based on a thiophene that reacts to generate a head-to-tail photoproduct. A co-crystal that exhibits both a homo- and heterosynthon in the same co-crystal based on adipic acid and the thiophene is also presented.

Noncentrosymmetric Packings Influenced by Electronic Properties of Products of Click Reactions

Co-reporter:Rebecca C. Laird, Nam P. Nguyen, Sara F. Rusch, Jonas Baltrusaitis, and Leonard R. MacGillivray

Crystal Growth & Design 2014 Volume 14(Issue 3) pp:893-896

Publication Date(Web):February 17, 2014

DOI:10.1021/cg4016542

Though 1,4-disubstituted 1,2,3-triazole rings have been utilized as electronic bridges in the solution phase, the use of a triazole ring to serve as an electronic bridge of small molecules in the crystalline state has been underdeveloped. Here two compounds with a central 1,4-disubstituted 1,2,3-triazole ring are synthesized to investigate the electronic bridging between terminal stilbazole and pyridine groups in the crystalline phase. The electronic properties of the molecules are characterized through solution phase UV–vis spectroscopy, single crystal X-ray diffractions, and density-of-state and gas-phase DFT calculations. We show that the electronic bridging behavior of a 1,4-disubstituted 1,2,3-triazole ring derived from a click reaction is maintained in the solid state by rare head-to-head (hh) packing in noncentrosymmetric crystal environments.

Synthon Hierarchies in Crystal Forms Composed of Theophylline and Hydroxybenzoic Acids: Cocrystal Screening via Solution-Mediated Phase Transformation

Co-reporter:Dejan-Krešimir Bučar, Rodger F. Henry, Geoff G. Z. Zhang, and Leonard R. MacGillivray

Crystal Growth & Design 2014 Volume 14(Issue 10) pp:5318-5328

Publication Date(Web):August 19, 2014

DOI:10.1021/cg501204k

Theophylline, a pharmaceutical model compound, was screened for cocrystal formation using nine (di)hydroxybenzoic acids as cocrystal formers, namely, 2-, 3-, 4-hydroxybenzoic- and 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, and 3,5-dihydroxybenzoic acids. The experiments were conducted using an efficient, reliable, and fast screening method based on thermodynamically driven solution-mediated phase transformation and revealed the formation of eight cocrystals and one salt. The theophylline-based solids were identified using powder and structurally characterized via single-crystal X-ray diffraction. The obtained solids are sustained by theopylline-carboxylic acid heterosynthons, in addition to both theophylline and carboxylic acid homosynthons. The results are a part of a systematic study of xanthine-alkaloid cocrystals that aims to establish synthon hierarchies in cocrystals comprised of molecules with multiple hydrogen-bonding functional groups. Structural features and synthon hierachies are discussed and compared to those in a series of published caffeine cocrystals.

From co-crystals to functional thin films: photolithography using [2+2] photodimerization

Co-reporter:Suman Ghorai, Joseph C. Sumrak, Kristin M. Hutchins, Dejan-Krešimir Bučar, Alexei V. Tivanski and Leonard R. MacGillivray

Chemical Science 2013 vol. 4(Issue 11) pp:4304-4308

Publication Date(Web):11 Sep 2013

DOI:10.1039/C3SC51073E

An approach to form organic thin films that employs multicomponent solids in the form of co-crystals has been developed. The components direct an intermolecular [2+2] photodimerization that we demonstrate exhibits a change in solubility that can be exploited as a negative photoresist for use in photolithography.

Single-crystal-to-single-crystal direct cross-linking and photopolymerisation of a discrete Ag(I) complex to give a 1D polycyclobutane coordination polymer

Co-reporter:Saikat Dutta, Dejan-Krešimir Bučar, Elizabeth Elacqua and Leonard R. MacGillivray

Chemical Communications 2013 vol. 49(Issue 11) pp:1064-1066

Publication Date(Web):22 Nov 2012

DOI:10.1039/C2CC36458A

A discrete dinuclear Ag(I) complex undergoes a single-crystal-to-single-crystal transformation to generate a 1D coordination polymer with a polycyclobutane backbone.

A Product of a Templated Solid-State Photodimerization Acts as a Template: Single-Crystal Reactivity in a Single Polymorph of a Cocrystal

Co-reporter:Suman Bhattacharya, Jelena Stojaković, Binoy K. Saha, and Leonard R. MacGillivray

Organic Letters 2013 Volume 15(Issue 4) pp:744-747

Publication Date(Web):January 25, 2013

DOI:10.1021/ol303283s

The concept of using a product of a template-directed solid-state reaction as a template is demonstrated. A cyclobutane lined with four carboxylic acid groups is employed as the template in photoreactive cocrystals. The resulting material is shown to exhibit polymorphism.

Supramolecular Complexes of Sulfadiazine and Pyridines: Reconfigurable Exteriors and Chameleon-like Behavior of Tautomers at the Co-Crystal–Salt Boundary

Co-reporter:Elizabeth Elacqua, Dejan-Krešimir Bučar, Rodger F. Henry, Geoff G. Z. Zhang, and Leonard R. MacGillivray

Crystal Growth & Design 2013 Volume 13(Issue 1) pp:393-403

Publication Date(Web):December 5, 2012

DOI:10.1021/cg301745x

We apply crystal engineering principles to prepare organic co-crystals and salts of sulfadiazine and pyridines. Pyridines are molecular building blocks utilized in crystal engineering that can disrupt the hydrogen bonded (amidine) N–H···N (pyrimidine) dimer within the parent sulfa drug (SD) crystals, while providing access to both co-crystals and salts. We have synthesized four co-crystals and three salts of sulfadiazine involving N,N-dimethyl-4-aminopyridine, 4-aminopyridine, 4-picoline, 4,4′-bipyridine, (E)-1,2-bis(4-pyridyl)ethylene, 1,2-bis(4-pyridyl)acetylene, and 4-(pyridin-4-yl)piperazine. Single-crystal X-ray analyses reveal three hydrogen-bond motifs, namely, dyads, rings, and chains based involving either (amidine/aniline) N–H···N (pyridine/pyrimidine), (pyridinium) +N–H···N– (amidide), (aniline/piperazine) N–H···O2S (sulfoxide) interactions, or a combination thereof. The hydrogen-bond motifs are assigned as D11(2), R22(8), R22(20), C22(17), and C22(13) graph sets. An analysis of the Cambridge Structural Database (CSD) reveals that the S–N bond length is generally shorter in complexes based on an anionic SD, which is consistent with the sulfonamide possessing greater S═N character. From an analysis of SD-based structures involving our work and the CSD, we present a heretofore not discussed role of tautomers at the co-crystal–salt boundary. Specifically, the ability of tautomeric forms of SDs to display reconfigurable exteriors, and thereby act as chameleons, enables SDs to accommodate different co-formers by assuming different geometries and adopting different regions along the co-crystal–salt boundary.

‘Masked synthons’ in crystal engineering: insulated components in acetaminophen cocrystal hydrates

Co-reporter:John R. G. Sander, Dejan-Krešimir Bučar, Rodger F. Henry, Brittany N. Giangiorgi, Geoff G. Z. Zhang and Leonard R. MacGillivray

CrystEngComm 2013 vol. 15(Issue 24) pp:4816-4822

Publication Date(Web):01 Feb 2013

DOI:10.1039/C3CE40159F

A series of cocrystals of acetaminophen and trans-1,2-bis(4-pyridyl)ethylene are reported wherein there is a lack of direct hydrogen-bonding between the components owing to interjected water molecules. A survey of the Cambridge Structural Database demonstrates that interjected water molecules involving cocrystals with similar components are rare. We term the lack of interaction as a ‘masked synthon’, which we aim to contribute to the development of synthon theory in organic solid-state chemistry.

Discrete Double-to-Quadruple Aromatic Stacks: Stepwise Integration of Face-to-Face Geometries in Cocrystals Based on Indolocarbazole

Co-reporter:Jelena Stojakovi&x107;;Avery M. Whitis ;Dr. Leonard R. MacGillivray

Angewandte Chemie 2013 Volume 125( Issue 46) pp:12349-12352

Publication Date(Web):

DOI:10.1002/ange.201304615

Discrete Double-to-Quadruple Aromatic Stacks: Stepwise Integration of Face-to-Face Geometries in Cocrystals Based on Indolocarbazole

Co-reporter:Jelena Stojakovi&x107;;Avery M. Whitis ;Dr. Leonard R. MacGillivray

Angewandte Chemie International Edition 2013 Volume 52( Issue 46) pp:12127-12130

Publication Date(Web):

DOI:10.1002/anie.201304615

Organic Nanocrystals of the Resorcinarene Hexamer via Sonochemistry: Evidence of Reversed Crystal Growth Involving Hollow Morphologies

Co-reporter:John R. G. Sander ; Dejan-Krešimir Bučar ; Jonas Baltrusaitis

Journal of the American Chemical Society 2012 Volume 134(Issue 16) pp:6900-6903

Publication Date(Web):February 13, 2012

DOI:10.1021/ja211141p

Nano- and micrometer-scale crystals of a self-assembled hexamer have been synthesized via sonochemistry. The application of ultrasonic irradiation afforded hollow rhombic-dodecahedral crystals of the C-methylcalix[4]resorcinarene hexamer. The formation of the hollow crystals is attributed to a reversed crystal growth mechanism heretofore described only in the synthesis of inorganic-based materials.

A [2+2] cross-photodimerisation of photostable olefinsvia a three-component cocrystal solid solution

Co-reporter:Dejan-Krešimir Bučar, Arundhuti Sen, S. V. Santhana Mariappan and Leonard R. MacGillivray

Chemical Communications 2012 vol. 48(Issue 12) pp:1790-1792

Publication Date(Web):03 Jan 2012

DOI:10.1039/C2CC15453F

A ditopic hydrogen-bond-donor template in the form of resorcinol facilitates a [2+2] cross-photodimerisation of 4-Cl-stilbazole and 4-Me-stilbazole in a rare cocrystal solid solution. A photoreaction does not proceed with the olefins individually or as a solid solution composed solely of the two olefins.

Organic nanocrystals of [2.2]paracyclophanes achieved via sonochemistry: enhanced and red-shifted emission involving edge-to-face chromophores

Co-reporter:Elizabeth Elacqua, Paul T. Jurgens, Jonas Baltrusaitis and Leonard R. MacGillivray

CrystEngComm 2012 vol. 14(Issue 22) pp:7567-7571

Publication Date(Web):23 Aug 2012

DOI:10.1039/C2CE26000J

We have prepared organic nanocrystals of [2.2]paracyclophane (pCp) and tetrakis(4-pyridylcyclobutyl)[2.2]paracyclophane (tpcp) via sonochemistry. Both nanocrystals exhibit an enhanced fluorescence compared to dilute solution, while the tpcp nanocrystals also demonstrate a red-shifted fluorescence.

[2.2]Paracyclophane as a Target of the Organic Solid State: Emergent Properties via Supramolecular Construction

Co-reporter:Elizabeth Elacqua;Tomislav Fri&x161;&x10d;i&x107;

Israel Journal of Chemistry 2012 Volume 52( Issue 1-2) pp:53-59

Publication Date(Web):

DOI:10.1002/ijch.201100089

Abstract

In this account, we review the synthesis of [2.2]paracyclophanes in the organic solid state. Reactions in crystalline solids provide a means to obtain molecules with high degrees of stereocontrol that can also be unattainable in solution. We show that [2.2]paracyclophanes form in the solid state stereospecifically and in quantitative yield via intermolecular [2+2] double photodimerization reactions. The double cycloaddition that affords a paracyclophane in the solid state does not readily occur in solution. Small molecules in the form of hydrogen-bond-donor templates can provide access to [2.2]paracyclophanes in a solid by design. A [2.2]paracyclophane obtained using a hydrogen-bond template is shown to exhibit attractive optical properties and has been employed as a building block of a metal-organic framework (MOF).

A Supramolecular Protecting Group Strategy Introduced to the Organic Solid State: Enhanced Reactivity through Molecular Pedal Motion

Co-reporter:Elizabeth Elacqua;Dr. Poonam Kaushik; Ryan H. Groeneman;Dr. Joseph C. Sumrak;Dr. Dejan-Kre&x161;imir Bu&x10d;ar ; Leonard R. MacGillivray

Angewandte Chemie International Edition 2012 Volume 51( Issue 4) pp:1037-1041

Publication Date(Web):

DOI:10.1002/anie.201106842

A Supramolecular Protecting Group Strategy Introduced to the Organic Solid State: Enhanced Reactivity through Molecular Pedal Motion

Co-reporter:Elizabeth Elacqua;Dr. Poonam Kaushik; Ryan H. Groeneman;Dr. Joseph C. Sumrak;Dr. Dejan-Kre&x161;imir Bu&x10d;ar ; Leonard R. MacGillivray

Angewandte Chemie 2012 Volume 124( Issue 4) pp:1061-1065

Publication Date(Web):

DOI:10.1002/ange.201106842

Designregeln fr die Selbstorganisation: von einem ebenen Netzwerk zu einem archimedischen Krper

Co-reporter: Leonard R. MacGillivray

Angewandte Chemie 2012 Volume 124( Issue 5) pp:1136-1138

Publication Date(Web):

DOI:10.1002/ange.201107282

Design Rules: A Net and Archimedean Polyhedra Score Big for Self-Assembly

Co-reporter: Leonard R. MacGillivray

Angewandte Chemie International Edition 2012 Volume 51( Issue 5) pp:1110-1112

Publication Date(Web):

DOI:10.1002/anie.201107282

Thixotropic Hydrogel Derived from a Product of an Organic Solid-State Synthesis: Properties and Densities of Metal−Organic Nanoparticles

Co-reporter:Tamara D. Hamilton ; Dejan-Krešimir Bučar ; Jonas Baltrusaitis ; Douglas R. Flanagan ; Yingjian Li ; Suman Ghorai ; Alexei V. Tivanski

Journal of the American Chemical Society 2011 Volume 133(Issue 10) pp:3365-3371

Publication Date(Web):February 22, 2011

DOI:10.1021/ja106095w

Metallogels form from Cu(II) ions and tetratopic ligand rctt-1,2-bis(3-pyridyl)-3,4-bis(4-pyridyl)cyclobutane. The tetrapyridyl cyclobutane has been synthesized in the organic solid state. The gel forms with a variety of counteranions and gels water. The hydrogel is thixotropic and is composed of nanoscale metal−organic particles (NMOPs), a high surface area of which likely accounts for the gelation of the polar aqueous medium. A shear stress profile of the thixotropic hydrogel gave a yield value of 8.33 Pa. A novel combination of atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) is used to assess the densities of individual NMOPs. A density of 1.37 g/cm3 has been determined. A single-crystal X-ray diffraction study demonstrates the ability of the unsymmetrical cyclobutane 3,4′-tpcb to self-assemble with Cu(II) ions in [Cu2(hfac)4(3,4′-tpcb)]∞ (where hfac is hexafluoroacetylacetonate) to form a solvated 1D coordination polymer.

A solid-state trimerisation of a diene diacid affords a bicyclobutyl: reactant structure from X-ray powder data and product separation and structure determination viaco-crystallisation

Co-reporter:Manza B. J. Atkinson, Ivan Halasz, Dejan-Krešimir Bučar, Robert E. Dinnebier, S. V. Santhana Mariappan, Anatoliy N. Sokolov and Leonard R. MacGillivray

Chemical Communications 2011 vol. 47(Issue 1) pp:236-238

Publication Date(Web):31 Aug 2010

DOI:10.1039/C0CC02204G

A bicyclobutyl that bears six carboxylic acid groups results from a trimerisation of a diene diacid in the solid state. Powder X-ray diffraction and a co-crystallisation are used to solve the structure of the diene and elucidate the stereochemistry of the bicyclobutyl, respectively.

Softening and Hardening of Macro- and Nano-Sized Organic Cocrystals in a Single-Crystal Transformation

Co-reporter:Dr. Chana Karunatilaka;Dejan-Kre&x161;imir Bu&x10d;ar;Lindsay R. Ditzler;Dr. Tomislav Fri&x161;&x10d;i&x107;;Dale C. Swenson;Dr. Leonard R. MacGillivray;Dr. Alexei V. Tivanski

Angewandte Chemie 2011 Volume 123( Issue 37) pp:8801-8805

Publication Date(Web):

DOI:10.1002/ange.201102370

Crystal engineering rescues a solution organic synthesis in a cocrystallization that confirms the configuration of a molecular ladder

Co-reporter:Manza B. J. Atkinson;S. V. Santhana Mariappan;Dejan-Krešimir Bučar;Jonas Baltrusaitis;Tomislav Friščić;Naif G. Sinada;

Proceedings of the National Academy of Sciences 2011 108(27) pp:10974-10979

Publication Date(Web):June 20, 2011

DOI:10.1073/pnas.1104352108

Treatment of an achiral molecular ladder of C_2h symmetry composed of five edge-sharing cyclobutane rings, or a [5]-ladderane, with acid results in cis- to trans-isomerization of end pyridyl groups. Solution NMR spectroscopy and quantum chemical calculations support the isomerization to generate two diastereomers. The NMR data, however, could not lead to unambiguous configurational assignments of the two isomers. Single-crystal X-ray diffraction was employed to determine each configuration. One isomer readily crystallized as a pure form and X-ray diffraction revealed the molecule as being achiral based on C_i symmetry. The second isomer resisted crystallization under a variety of conditions. Consequently, a strategy based on a cocrystallization was developed to generate single crystals of the second isomer. Cocrystallization of the isomer with a carboxylic acid readily afforded single crystals that confirmed a chiral ladderane based on C₂ symmetry. The chiral ladderane and acid self-assembled to generate a five-component hydrogen-bonded complex that packs to form large solvent-filled homochiral channels of nanometer-scale dimensions. Whereas cocrystallizations are frequently applied to structure determinations of proteins, our study represents the first application of a cocrystallization to confirm the relative configuration of a small-molecule diastereomer generated in a solution-phase organic synthesis.

Softening and Hardening of Macro- and Nano-Sized Organic Cocrystals in a Single-Crystal Transformation

Co-reporter:Dr. Chana Karunatilaka;Dejan-Kre&x161;imir Bu&x10d;ar;Lindsay R. Ditzler;Dr. Tomislav Fri&x161;&x10d;i&x107;;Dale C. Swenson;Dr. Leonard R. MacGillivray;Dr. Alexei V. Tivanski

Angewandte Chemie International Edition 2011 Volume 50( Issue 37) pp:8642-8646

Publication Date(Web):

DOI:10.1002/anie.201102370

Conformational polymorphism facilitates assignment of trans and cis-conformers of an α-substituted oligothiophene via IR spectroscopy

Co-reporter:Anatoliy N. Sokolov, Joseph C. Sumrak and Leonard R. MacGillivray

Chemical Communications 2010 vol. 46(Issue 1) pp:82-84

Publication Date(Web):19 Oct 2009

DOI:10.1039/B915609G

Conformational polymorphism is exploited as a means to assign cis–trans and trans–trans conformations of an oligothiophene backbone using solid-state IR spectroscopy.

Stereospecific and quantitative photodimerisation of terminal olefins in the solid state

Co-reporter:Ivan G. Georgiev, Dejan-Krešimir Bučar and Leonard R. MacGillivray

Chemical Communications 2010 vol. 46(Issue 27) pp:4956-4958

Publication Date(Web):01 Jun 2010

DOI:10.1039/C0CC01184C

Reaction of 4-vinylpyridine with AgClO3 yields a crystalline solid that supports a stereospecific and quantitative [2+2] photodimerisation of two terminal olefins. Structural dynamics of the −CHCH2 group, nature of the counterion, and extended packing influence the photoreactivity.

A metal–organic framework with three cavities based on three-coloured square tiling derived from a cyclobutane constructed in the solid state

Co-reporter:Tamara D. Hamilton, Dejan-Krešimir Bučar and Leonard R. MacGillivray

New Journal of Chemistry 2010 vol. 34(Issue 11) pp:2400-2402

Publication Date(Web):09 Aug 2010

DOI:10.1039/C0NJ00367K

The unsymmetrical tetratopic ligand rctt-1,2-bis(3-pyridyl)-3,4-bis(4-pyridyl)cyclobutane self-assembles with zinc(II) nitrate to form a 2D metal–organic framework with three distinct cavities.

From the Decks to the Bridges: Optoelectronics in [2.2]Paracyclophane Chemistry

Co-reporter:Elizabeth Elacqua

European Journal of Organic Chemistry 2010 Volume 2010( Issue 36) pp:6883-6894

Publication Date(Web):

DOI:10.1002/ejoc.201000930

Abstract

In this microreview, we highlight optical properties of [2.2]paracyclophanes (pCps). We demonstrate how the spectroscopic properties that stem from the strained and π-stacked structure have resulted in pCps being incorporated in materials science and polymer synthesis. As a result of chromophore substitution, internal charge transfer (ICT) between the two rings of the cyclophane core produce frameworks with unique optical properties. Deck-substituted molecules and polymers have beensynthesized that possess donor and acceptor groups that affect internal charge transfer (ICT). We also demonstrate that bridge-substituted [2.2]paracylophanes, although not well studied in this context, display unexpected optical properties owing to nonconventional ICT. A highlight is a recent templated solid-state synthesis that affords a pCp that exhibits dramatic red-shifted fluorescence.

Supramolecular Catalysis in the Organic Solid State through Dry Grinding

Co-reporter:AnatoliyN. Sokolov Dr.;Dejan-Kre&x161;imir Bu&x10d;ar;Jonas Baltrusaitis Dr.;SeanX. Gu;LeonardR. MacGillivray Dr.

Angewandte Chemie 2010 Volume 122( Issue 25) pp:4369-4373

Publication Date(Web):

DOI:10.1002/ange.201000874

Supramolecular Catalysis in the Organic Solid State through Dry Grinding

Co-reporter:AnatoliyN. Sokolov Dr.;Dejan-Kre&x161;imir Bu&x10d;ar;Jonas Baltrusaitis Dr.;SeanX. Gu;LeonardR. MacGillivray Dr.

Angewandte Chemie International Edition 2010 Volume 49( Issue 25) pp:4273-4277

Publication Date(Web):

DOI:10.1002/anie.201000874

A 1:1 Cocrystal of Caffeine and 2-Hydroxy-1-Naphthoic Acid Obtained via a Slurry Screening Method

Co-reporter:Dejan-Krešimir Bučar;Rodger F. Henry

Journal of Chemical Crystallography 2010 Volume 40( Issue 11) pp:933-939

Publication Date(Web):2010 November

DOI:10.1007/s10870-010-9766-y

A cocrystal of caffeine (caf) and 2-hydroxy-1-naphthoic acid (2H1NA), namely, (caf)·(2H1NA), was discovered via a screening method based on solution-mediated phase transformation (SMPT). The components crystallize as a two-component hydrogen-bonded assembly involving both an intermolecular O–H···N and intramolecular O–H···O hydrogen bond. The assemblies stack parallel and offset. Crystal data: monoclinic P 21/n space group, a = 7.909(2) Å, b = 15.275(5) Å, c = 14.704(5) Å, β = 103.66(1)°, Z = 4, V = 1726.1(9) Å3, Dc = 1.471 g/cm3 and R1 = 0.081, wR2 = 0.163. The cocrystal (caf)·(2H1NA) was also subjected to polymorph screening using 15 different solvents, with all resulting solids being identified as the original form.

Pharmaceutical Nano-Cocrystals: Sonochemical Synthesis by Solvent Selection and Use of a Surfactant

Co-reporter:John R. G. Ser;Dejan-Kre&x161;imir Bu&x10d;ar;Rodger F. Henry;Dr. Geoff G. Z. Zhang; Leonard R. MacGillivray

Angewandte Chemie International Edition 2010 Volume 49( Issue 40) pp:7284-7288

Publication Date(Web):

DOI:10.1002/anie.201002588

Dramatic Red-Shifted Fluorescence of [2.2]Paracyclophanes with Peripheral Substituents Attached to the Saturated Bridges

Co-reporter:Elizabeth Elacqua, Dejan-Krešimir Bučar, Yulia Skvortsova, Jonas Baltrusaitis, M. Lei Geng and Leonard R. MacGillivray

Organic Letters 2009 Volume 11(Issue 22) pp:5106-5109

Publication Date(Web):October 23, 2009

DOI:10.1021/ol901907j

A bridge-substituted [2.2]paracyclophane obtained from the organic solid state exhibits a dramatic red shift in fluorescence relative to [2.2]paracyclophane. A further red shift occurs upon alkylation of the pyridylcyclobutyl bridges. Our results demonstrate that [2.2]cyclophanes substituted at the bridge, despite not being attached via the extended π-system, are promising building blocks in the development of optical materials.

Engineering cocrystal and polymorph architecture via pseudoseeding

Co-reporter:Tomislav Friščić and Leonard R. MacGillivray

Chemical Communications 2009 (Issue 7) pp:773-775

Publication Date(Web):14 Jan 2009

DOI:10.1039/B820120J

We use a cocrystal with components arranged in a 1D hydrogen-bonded chain as a pseudoseed to template the components of a cocrystal that otherwise forms a photoactive 0D assembly to form a photostable 1D chain structure.

Cocrystals of Caffeine and Hydroxybenzoic Acids Composed of Multiple Supramolecular Heterosynthons: Screening via Solution-Mediated Phase Transformation and Structural Characterization

Co-reporter:Dejan-Krešimir Bučar, Rodger F. Henry, Xiaochun Lou, Richard W. Duerst, Leonard R. MacGillivray and Geoff G. Z. Zhang

Crystal Growth & Design 2009 Volume 9(Issue 4) pp:1932-1943

Publication Date(Web):March 5, 2009

DOI:10.1021/cg801178m

Caffeine, a pharmaceutical model compound, generally forms cocrystals with carboxylic acids that involve an O−H···N hydrogen bond between the carboxylic acid group of the acid and the caffeine imidazole moiety. Such solids are typically based on a single heterosynthon. To examine the facility of introducing additional supramolecular heterosynthons to the caffeine-carboxylic-acid cocrystal system, structural isomers of aromatic carboxylic acids (i.e., hydroxy- and dihydroxybenzoic acids) with additional hydrogen-bonding functional groups (i.e., hydroxy group) were screened for cocrystal formation. For this purpose, a highly efficient screening method based on thermodynamically driven solution-mediated phase transformation was utilized. This method enabled the rapid discovery of nine new solid phases involving caffeine. These caffeine phases were identified using single-crystal X-ray diffraction and FT-IR spectroscopy as cocrystals based on 2-, 3-, 4-hydroxybenzoic- and 2,3-, 2,4-, 2,5-, 3,4-, and 3,5-dihydroxybenzoic acids. Structural analyses of the cocrystals revealed solids composed of up to three caffeine−carboxylic acid heterosynthons.

Supramolecular Control of Reactivity in the Solid State: From Templates to Ladderanes to Metal−Organic Frameworks

Co-reporter:Leonard R. MacGillivray, Giannis S. Papaefstathiou, Tomislav Friščić, Tamara D. Hamilton, Dejan-Krešimir Bučar, Qianli Chu, Dushyant B. Varshney and Ivan G. Georgiev

Accounts of Chemical Research 2008 Volume 41(Issue 2) pp:280

Publication Date(Web):February 19, 2008

DOI:10.1021/ar700145r

We describe how reactivity can be controlled in the solid state using molecules and self-assembled metal−organic complexes as templates. Being able to control reactivity in the solid state bears relevance to synthetic chemistry and materials science. The former offers a promise to synthesize molecules that may be impossible to realize from the liquid phase while also taking advantage of the benefits of conducting highly stereocontrolled reactions in a solvent-free environment (i.e., green chemistry). The latter provides an opportunity to modify bulk physical properties of solids (e.g., optical properties) through changes to molecular structure that result from a solid-state reaction. Reactions in the solid state have been difficult to control owing to frustrating effects of molecular close packing. The high degree of order provided by the solid state also means that the templates can be developed to determine how principles of supramolecular chemistry can be generally employed to form covalent bonds. The paradigm of synthetic chemistry employed by Nature is based on integrating noncovalent and covalent bonds. The templates assemble olefins via either hydrogen bond or coordination-driven self-assembly for intermolecular [2 + 2] photodimerizations. The olefins are assembled within discrete, or finite, self-assembled complexes, which effectively decouples chemical reactivity from effects of crystal packing. The control of the solid-state assembly process affords the supramolecular construction of targets in the form of cyclophanes and ladderanes. The targets form stereospecifically, in quantitative yield, and in gram amounts. Both [3]- and [5]-ladderanes have been synthesized. The ladderanes are comparable to natural ladderane lipids, which are a new and exciting class of natural products recently discovered in anaerobic marine bacteria. The organic templates function as either hydrogen bond donors or hydrogen bond acceptors. The donors and acceptors generate cyclobutanes lined with pyridyl and carboxylic acid groups, respectively. The metal−organic templates are based on Zn(II) and Ag(I) ions. The reactivity involving Zn(II) ions is shown to affect optical properties in the form of solid-state fluorescence. The solids based on both the organic and metal−organic templates undergo rare single-crystal-to-single-crystal reactions. We also demonstrate how the cyclobutanes obtained from this method can be applied as novel polytopic ligands of metallosupramolecular assemblies (e.g., self-assembled capsules) and materials (e.g., metal−organic frameworks). Sonochemistry is also used to generate nanostructured single crystals of the multicomponent solids or cocrystals based on the organic templates. Collectively, our observations suggest that the organic solid state can be integrated into more mainstream settings of synthetic organic chemistry and be developed to construct functional crystalline solids.

General application of mechanochemistry to templated solid-state reactivity: rapid and solvent-free access to crystalline supermolecules

Co-reporter:Manza B. J. Atkinson, Dejan-Krešimir Bučar, Anatoliy N. Sokolov, Tomislav Friščić, Chanceity N. Robinson, Mahmood Y. Bilal, Naif G. Sinada, Asher Chevannes and Leonard R. MacGillivray

Chemical Communications 2008 (Issue 44) pp:5713-5715

Publication Date(Web):30 Sep 2008

DOI:10.1039/B812728J

Supermolecules with olefins organized by hydrogen-bond donor and acceptor templates and that react in the solid state rapidly form co-crystals via solvent-free and liquid-assisted grinding.

A lanthanide-based helicate coordination polymer derived from a rigid monodentate organic bridge synthesized in the solid state

Co-reporter:Dejan-Krešimir Bučar, Giannis S. Papaefstathiou, Tamara D. Hamilton and Leonard R. MacGillivray

New Journal of Chemistry 2008 vol. 32(Issue 5) pp:797-799

Publication Date(Web):25 Mar 2008

DOI:10.1039/B800878G

Tetratopic rctt-tetrakis(4-pyridyl)cyclobutane acts as an angular bifunctional ligand that yields a single-stranded helicate coordination polymer based on a Ln(III) ion.

Conformational polymorphism in a heteromolecular single crystal leads to concerted movement akin to collective rack-and-pinion gears at the molecular level

Co-reporter:Anatoliy N. Sokolov;Dale C. Swenson

PNAS 2008 Volume 105 (Issue 6 ) pp:1794-1797

Publication Date(Web):2008-02-12

DOI:10.1073/pnas.0706117105

We describe a heteromolecular single crystal that exhibits three reversible and concerted reorganizations upon heating and cooling. The products of the reorganizations are conformational polymorphs. The reorganizations are postulated to proceed through three motions: (i) alkyl translations, (ii) olefin rotations, and (iii) rotational tilts. The motions are akin to rack-and-pinion gears at the molecular level. The rack-like movement is based on expansions and compressions of alkyl chains that are coupled with pinion-like 180° rotations of olefins. To accommodate the movements, phenol and thiophene components undergo rotational tilts about intermolecular hydrogen bonds. The movements are collective, being propagated in close-packed repeating units. This discovery marks a step to understanding how organic solids can support the development of crystalline molecular machines and devices through correlated and collective movements.

Metal-mediated reactivity in the organic solid state: from self-assembled complexes to metal–organic frameworks

Co-reporter:Ivan G. Georgiev and Leonard R. MacGillivray

Chemical Society Reviews 2007 vol. 36(Issue 8) pp:1239-1248

Publication Date(Web):08 May 2007

DOI:10.1039/B516074J

The purpose of this tutorial review is to address the use of metal ions to mediate reactions in the organic solid state. We describe metal complexes and coordination networks that facilitate dimerizations, oligomerizations and polymerizations of olefins and acetylenes via irradiation (e.g. ultraviolet (UV) and 60Co γ-rays) and thermal annealing. We show how metal ions can be utilized to direct the formation of polymers and molecules. We also describe how supramolecular chemistry has recently influenced dimerization processes in self-assembled metal–organic solids.

Coding a coordination-driven self-assembly via a hydrogen bond-directed solid-state synthesis: An unexpected chiral tetrahedral capsule

Co-reporter:Tamara D. Hamilton, Dejan-Krešimir Bučar and Leonard R. MacGillivray

Chemical Communications 2007 (Issue 16) pp:1603-1604

Publication Date(Web):21 Mar 2007

DOI:10.1039/B700748E

An achiral ligand, synthesized in the solid state via a coded hydrogen bond-directed organic synthesis, self-assembles with Cu(II) ions to form a chiral tetrahedral capsule that hosts an anion as a guest.

Template-Controlled Reactivity in the Organic Solid State by Principles of Coordination-Driven Self-Assembly

Co-reporter:Dejan-Krešimir Bučar;Giannis S. Papaefstathiou;Tamara D. Hamilton;Qianli L. Chu;Ivan G. Georgiev

European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 29) pp:

Publication Date(Web):14 SEP 2007

DOI:10.1002/ejic.200700442

In this microreview, we show how principles of coordination-driven self-assembly can be used to direct chemical reactivity in the organic solid state. We also show how products obtained from the templated solid-state reactions can be used as organic building units of metal–organic frameworks and coordination capsules. Self-assembled structures based on dinuclear Zn^II and Ag^I complexes are used to direct stereocontrolled [2+2] photodimerizations of vinylpyridines in the solid state in up to quantitative yield. The products are used as bi- and polytopic ligands of self-assembled coordination capsules and metal–organic frameworks. We also describe emerging metal-based approaches to conduct mechanochemical reactions in organic solids. In addition to the field of supramolecular coordination chemistry, these observations impact the field of green chemistry.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Crystal and Molecular Structure of trans-1,2-bis(2-benzothiazolyl)ethene

Co-reporter:Poonam Kaushik;Dejan-Krešimir Bučar

Journal of Chemical Crystallography 2007 Volume 37( Issue 10) pp:713-715

Publication Date(Web):2007 October

DOI:10.1007/s10870-007-9238-1

The crystal and molecular structure of trans-1,2-bis(2-benzothiazolyl)ethene is reported. Crystal data for 1: monoclinic, space group C 2/c, a = 24.926(3) Å, b = 4.843(1) Å, c = 11.164(1) Å, β = 105.274(5) °, V = 1300.0(3) Å3, and Dc = 1.50 g/cm3 for Z = 4 and R = 0.028. The molecule crystallizes in the form of a colorless plate and forms one-dimensional slipped π-stacks.

Heteroditopic Rebek's Imide Directs the Reactivity of Homoditopic Olefins within Desolvated Quaternary Assemblies in the Solid State

Co-reporter:Dushyant B. Varshney;Xiuchun Gao;Tomislav Friščić

Angewandte Chemie 2006 Volume 118(Issue 4) pp:

Publication Date(Web):19 DEC 2005

DOI:10.1002/ange.200502294

Eine seltene Einkristall-Einkristall-Transformation hat die [2+2]-Photodimerisierung homoditoper Olefine (trans-1,2-Bis(4-pyridyl)ethylen) zur Folge, die mithilfe von Rebeks Imid in H-Brücken-gebundenen Komplexen zusammengeführt und vororganisiert wurden. Dabei entsteht ein rctt-Tetrakis(4-pyridyl)cyclobutan (siehe Bild) stereospezifisch mit bis zu 100 % Ausbeute.

Heteroditopic Rebek's Imide Directs the Reactivity of Homoditopic Olefins within Desolvated Quaternary Assemblies in the Solid State

Co-reporter:Dushyant B. Varshney, Xiuchun Gao, Tomislav Fri&x161;&x10d;i&x107;,Leonard R. MacGillivray

Angewandte Chemie International Edition 2006 45(4) pp:646-650

Publication Date(Web):

DOI:10.1002/anie.200502294

Reversing the code of a template-directed solid-state synthesis: a bipyridine template that directs a single-crystal-to-single-crystal [2 + 2] photodimerisation of a dicarboxylic acid

Co-reporter:Tomislav Friščić and Leonard R. MacGillivray

Chemical Communications 2005 (Issue 46) pp:5748-5750

Publication Date(Web):20 Oct 2005

DOI:10.1039/B510081J

A linear template in the form of a bipyridine has been developed and is shown to direct a single-crystal-to-single-crystal [2 + 2] photodimerisation of a dicarboxylic acid.

Directed assembly and reactivity of olefins within a one-dimensional ladder-like coordination polymer based on a dinuclear Zn(II) platform

Co-reporter:Giannis S. Papaefstathiou, Ivan G. Georgiev, Tomislav Friščić and Leonard R. MacGillivray

Chemical Communications 2005 (Issue 31) pp:3974-3976

Publication Date(Web):08 Jul 2005

DOI:10.1039/B504477D

A ladder-like coordination polymer involving a dinuclear Zn Schiff-base complex possesses organic linkers that undergo [2 + 2] photodimerisation in the solid state.

Template-controlled reactivity: Following nature's way to design and construct metal-organic polyhedra and polygons

Co-reporter:Tamara D. Hamilton, Giannis S. Papaefstathiou, Leonard R. MacGillivray

Journal of Solid State Chemistry 2005 Volume 178(Issue 8) pp:2409-2413

Publication Date(Web):August 2005

DOI:10.1016/j.jssc.2005.05.034

We show how a template-controlled reaction performed in the organic solid state can be used to construct a molecule that functions as an organic building unit of both a metal-organic polyhedron and polygon. The template is a small organic molecule that organizes two olefins via hydrogen bonds for a [2+2] photodimerization. The process of utilizing a molecule to build a molecule that is subsequently used for self-assembly is inspired by the general two-step process of template-directed synthesis and self-assembly of Nature that is used to construct large, functional self-assembled structures.A metal-organic polygon and polyhedron are obtained from a molecule constructed in the organic solid state using a linear template.

A Single-Crystal-to-Single-Crystal Transformation Mediated by Argentophilic Forces Converts a Finite Metal Complex into an Infinite Coordination Network

Co-reporter:Qianli Chu;Dale C. Swenson Dr.

Angewandte Chemie International Edition 2005 Volume 44(Issue 23) pp:

Publication Date(Web):4 MAY 2005

DOI:10.1002/anie.200500400

Reactions in crystals: Interactions between Ag^I ions are used to preorganize olefins for a regiocontrolled single-crystal-to-single-crystal (SCSC) [2+2] photodimerization that results in a quantitative conversion of a finite dinuclear complex into a one-dimensional coordination network (see scheme).

A Single-Crystal-to-Single-Crystal Transformation Mediated by Argentophilic Forces Converts a Finite Metal Complex into an Infinite Coordination Network

Co-reporter:Qianli Chu;Dale C. Swenson Dr.

Angewandte Chemie 2005 Volume 117(Issue 23) pp:

Publication Date(Web):4 MAY 2005

DOI:10.1002/ange.200500400

Reaktionen in Kristallen: Wechselwirkungen zwischen Ag^I-Ionen dienen dazu, Olefine für eine regiokontrollierte Einkristall-Einkristall(SCSC)-[2+2]-Photodimerisierung vorzuorientieren, bei der ein endlicher zweikerniger Komplex quantitativ in ein eindimensionales Koordinationsnetzwerk überführt wird (siehe Schema).

Self-assembled metal–organic squares derived from linear templates as exemplified by a polydentate ligand that provides access to both a polygon and polyhedron

Co-reporter:Giannis S. Papaefstathiou, Tamara D. Hamilton, Tomislav Friščić and Leonard R. MacGillivray

Chemical Communications 2004 (Issue 3) pp:270-271

Publication Date(Web):07 Jan 2004

DOI:10.1039/B313435K

Di- 1a and tetranuclear 1b metal–organic squares have been obtained from bis- and tetra(pyridyl)cyclobutanes synthesized in the solid state, respectively; for 1b, a cyclobutane with two different metal binding subunits supports the formation of a polygon and polyhedron.

A 2D metal-organic framework with two different rhombus-shaped cavities: a rare example of a (4,4)-net with alternating metal and organic nodes

Co-reporter:Giannis S Papaefstathiou, Costas Milios, Leonard R MacGillivray

Microporous and Mesoporous Materials 2004 Volume 71(1–3) pp:11-15

Publication Date(Web):17 June 2004

DOI:10.1016/j.micromeso.2004.03.008

The synthesis and crystal structure of the metal-organic framework {[Co(acetate)2(rctt-tetrakis(4-pyridyl)cyclobutane)] · 2(methanol)}∞ (1) are described. The structure of 1 is based on a (4,4)-grid topology with Co(II) ions and 4,4′-tpcb cyclobutane molecules as 4-connected nodes and two different rhombus-shaped cavities in the framework. Solvent methanol molecules are clathrated between the grids. A model involving pseudo-merohedral twinning was required to arrive at a satisfactory single-crystal structure solution. Crystal data for 1: triclinic, space group P, a=9.006(2), b=9.127(2), c=9.129(2), α=78.57(3), β=88.99(3), γ=88.98(3), V=735.4(3), and Z=1 for R=0.0362 (2539 reflections with I>2σ(I), 184 parameters).

Supramolecular Construction of Molecular Ladders in the Solid State

Co-reporter:Xiuchun Gao;Tomislav Friščić

Angewandte Chemie 2004 Volume 116(Issue 2) pp:

Publication Date(Web):5 NOV 2003

DOI:10.1002/ange.200352713

Stufen in der supramolekularen Chemie: Lineare Templatverbindungen wurden zum Formen von Polyenen im festen Zustand durch Wasserstoffbrückenbindungen eingesetzt. Die Polyene dimerisieren in einer [2+2]-Photocycloaddition quantitativ zu [3]- und [5]-Ladderanen (das Bild zeigt das so erhaltene [5]-Ladderan).

Titelbild: Supramolecular Construction of Molecular Ladders in the Solid State (Angew. Chem. 2/2003)

Co-reporter:Xiuchun Gao;Tomislav Friščić

Angewandte Chemie 2004 Volume 116(Issue 2) pp:

Publication Date(Web):19 DEC 2003

DOI:10.1002/ange.200390669

Supramolecular Construction of Molecular Ladders in the Solid State

Co-reporter:Xiuchun Gao;Tomislav Friščić

Angewandte Chemie International Edition 2004 Volume 43(Issue 2) pp:

Publication Date(Web):5 NOV 2003

DOI:10.1002/anie.200352713

Steps in supramolecular chemistry: Molecules in the form of linear templates have been used to preorganize polyenes in the solid state through hydrogen-bonding interactions. The polyenes can then undergo [2+2] photocycloaddition reactions to produce [3]- and [5]ladderanes in gram quantities and 100 % yield. (The picture shows the obtained [5]ladderane.)

Cover Picture: Supramolecular Construction of Molecular Ladders in the Solid State (Angew. Chem. Int. Ed. 2/2003)

Co-reporter:Xiuchun Gao;Tomislav Friščić

Angewandte Chemie International Edition 2004 Volume 43(Issue 2) pp:

Publication Date(Web):19 DEC 2003

DOI:10.1002/anie.200390642

‘Template-switching’: a supramolecular strategy for the quantitative, gram-scale construction of a molecular target in the solid state

Co-reporter:Tomislav Friščič and Leonard R. MacGillivray

Chemical Communications 2003 (Issue 11) pp:1306-1307

Publication Date(Web):06 May 2003

DOI:10.1039/B301726P

A template–switching strategy based on the modularity of template-directed solid-state synthesis has been successfully utilised to achieve a quantitative, stereospecific solid-state synthesis of a p-[2.2]-cyclophane target in gram quantities.

Site-directed regiocontrolled synthesis of a ‘head-to-head’ photodimer via a single-crystal-to-single-crystal transformation involving a linear template

Co-reporter:Dushyant B. Varshney, Giannis S. Papaefstathiou and Leonard R. MacGillivray

Chemical Communications 2002 (Issue 17) pp:1964-1965

Publication Date(Web):05 Aug 2002

DOI:10.1039/B204542G

Co-crystallisation of 1,8-naphthalenedicarboxylic acid (1,8-nap) with trans-1-(3-pyridyl)-2-(4-pyridyl)ethylene (3,4-bpe) gives a discrete molecular solid-state assembly, 2(3,4-bpe)·2(1,8-nap) 1, that is held together by four O–H⋯N hydrogen bonds wherein the diacid directs a regiocontrolled [2 + 2] photodimerization; the reaction occurs by way of a single-crystal-to-single-crystal transformation.

Discrete and infinite coordination arrays derived from a template-directed, solid-state, organic synthesis

Co-reporter:Tamara D. Hamilton, Giannis S. Papaefstathiou and Leonard R. MacGillivray

CrystEngComm 2002 vol. 4(Issue 41) pp:223-226

Publication Date(Web):15 Jul 2002

DOI:10.1039/B202169B

A product derived from a template-directed, organic, solid-state synthesis, rctt-tetrakis(2-pyridyl)cyclobutane (2,2′-tpcb), serves as a bis-chelating ligand upon reaction with Cu(NO3)2·2.5H2O and CuSO4·5H2O to produce discrete and infinite coordination arrays, [Cu2(NO3)4(μ-2,2′-tpcb)] (1) and [Cu2(μ2-SO4)2(μ-2,2′-tpcb)(H2O)2]n·9H2O (2), respectively.

From engineering crystals to engineering molecules: emergent consequences of controlling reactivity in the solid state using linear templates

Co-reporter:Leonard R. MacGillivray

CrystEngComm 2002 vol. 4(Issue 7) pp:37-41

Publication Date(Web):

DOI:10.1039/B200332E

Molecules that function as linear templates provide a means to organize two molecules, using the principles of molecular recognition and self-assembly, for a bimolecular reaction. The design and application of linear templates in order to direct reactivity in organic solids, particularly [2 + 2] photoreactivity, is outlined. The linear templates provide control of solid-state reactivity such that it is possible, in a similar way to the liquid phase, to conduct molecular synthesis by design.

An Inverted Metal-Organic Framework with Compartmentalized Cavities Constructed by Using an Organic Bridging Unit Derived from the Solid State

Co-reporter:Giannis S. Papaefstathiou

Angewandte Chemie International Edition 2002 Volume 41(Issue 12) pp:

Publication Date(Web):12 JUN 2002

DOI:10.1002/1521-3773(20020617)41:12<2070::AID-ANIE2070>3.0.CO;2-1

Gridlock: A porous metal–organic framework with an interior tailored supramolecularly with organic groups is described (see structure; two grids have been differentiated using cyan and gray, while the yellow spheres represent included methyl groups). The approach relies on inverting the role of a secondary building unit (SBU) and an organic linker such that the organic linker serves as a node and the SBU serves as a linear bridge. The organic node used to construct the framework has been obtained by way of a template-directed solid-state organic synthesis.

A Regiocontrolled ‘Head-to-Tail’ [2+2] Photodimerization of a Stilbene involving a Ternary Solid based on Catechol

Co-reporter:Giannis S. Papaefstathiou, Tomislav Friščić, Leonard R. MacGillivray

Journal of Supramolecular Chemistry 2002 Volume 2(1–3) pp:227-231

Publication Date(Web):January–June 2002

DOI:10.1016/S1472-7862(03)00077-7

Co-crystallization of 1,2-dihydroxybenzene (cat) with trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (2,4-bpe) gives a layered ternary solid, (cat)·(2,4-bpe)·(H2O) 1, with molecular components held together by a combination of O–H⋯N and O–H⋯O forces wherein 2,4-bpe is organized for a ‘head-to-tail’ (ht) [2+2] photocyclodimerization. UV-irradiation of the solid produces rctt-1,3-bis(2-pyridyl)-2,4-bis(4-pyridyl)cyclobutane [rctt-(2,4-tpcb-ht)] in quantitative yield. The structure of rctt-(2,4-tpcb-ht), in the form of crystalline rctt-(2,4-tpcb-ht)·1.5(H2O), has been confirmed by way of single-crystal X-ray diffraction.Graphic

Exploiting modularity in template-controlled synthesis: a new linear template to direct reactivity within discrete hydrogen-bonded molecular assemblies in the solid state

Co-reporter:Giannis S. Papaefstathiou, Alex J. Kipp and Leonard R. MacGillivray

Chemical Communications 2001 (Issue 23) pp:2462-2463

Publication Date(Web):07 Nov 2001

DOI:10.1039/B106584J

Co-crystallization of 1,8-naphthalenedicarboxylic acid (1,8-nap) with trans-1,2-bis(n-pyridyl)ethylene (n,n′-bpe) (n = 2 or 4) yields a discrete four-component molecular assembly, 2(n,n′-bpe)·2(1,8-nap) 1, that is held together by four O–H⋯N hydrogen bonds where the dicarboxylic acid, serving as a linear template, directs alignment of olefins in the solid state for [2 + 2] photoreaction.

Conformational isomerism leads to supramolecular isomerism and nanoscale inclusion in 2D extended framework solids based on C-methylcalix[4]resorcinarene

Co-reporter:Leonard R. MacGillivray, Jennifer L. Reid and John A. Ripmeester

Chemical Communications 2001 (Issue 11) pp:1034-1035

Publication Date(Web):09 May 2001

DOI:10.1039/B102856C

Co-crystallization of C-methylcalix[4]resorcinarene 1 with 4,4′-bipyridine 2 in the presence of m-xylene results in the formation of a 2D brick framework, 3c·2(m-xylene), that possesses nanoscale cavities that host four aromatics as guests in which 1 adopts a ‘T-shaped’ conformation.

Stereospecific and quantitative photodimerisation of terminal olefins in the solid state

Co-reporter:Ivan G. Georgiev, Dejan-Krešimir Bučar and Leonard R. MacGillivray

Chemical Communications 2010 - vol. 46(Issue 27) pp:NaN4958-4958

Publication Date(Web):2010/06/01

DOI:10.1039/C0CC01184C

Reaction of 4-vinylpyridine with AgClO3 yields a crystalline solid that supports a stereospecific and quantitative [2+2] photodimerisation of two terminal olefins. Structural dynamics of the −CHCH2 group, nature of the counterion, and extended packing influence the photoreactivity.

General application of mechanochemistry to templated solid-state reactivity: rapid and solvent-free access to crystalline supermolecules

Co-reporter:Manza B. J. Atkinson, Dejan-Krešimir Bučar, Anatoliy N. Sokolov, Tomislav Friščić, Chanceity N. Robinson, Mahmood Y. Bilal, Naif G. Sinada, Asher Chevannes and Leonard R. MacGillivray

Chemical Communications 2008(Issue 44) pp:NaN5715-5715

Publication Date(Web):2008/09/30

DOI:10.1039/B812728J

Supermolecules with olefins organized by hydrogen-bond donor and acceptor templates and that react in the solid state rapidly form co-crystals via solvent-free and liquid-assisted grinding.

Metal-mediated reactivity in the organic solid state: from self-assembled complexes to metal–organic frameworks

Co-reporter:Ivan G. Georgiev and Leonard R. MacGillivray

Chemical Society Reviews 2007 - vol. 36(Issue 8) pp:NaN1248-1248

Publication Date(Web):2007/05/08

DOI:10.1039/B516074J

The purpose of this tutorial review is to address the use of metal ions to mediate reactions in the organic solid state. We describe metal complexes and coordination networks that facilitate dimerizations, oligomerizations and polymerizations of olefins and acetylenes via irradiation (e.g. ultraviolet (UV) and 60Co γ-rays) and thermal annealing. We show how metal ions can be utilized to direct the formation of polymers and molecules. We also describe how supramolecular chemistry has recently influenced dimerization processes in self-assembled metal–organic solids.

A solid-state trimerisation of a diene diacid affords a bicyclobutyl: reactant structure from X-ray powder data and product separation and structure determination viaco-crystallisation

Co-reporter:Manza B. J. Atkinson, Ivan Halasz, Dejan-Krešimir Bučar, Robert E. Dinnebier, S. V. Santhana Mariappan, Anatoliy N. Sokolov and Leonard R. MacGillivray

Chemical Communications 2011 - vol. 47(Issue 1) pp:NaN238-238

Publication Date(Web):2010/08/31

DOI:10.1039/C0CC02204G

A bicyclobutyl that bears six carboxylic acid groups results from a trimerisation of a diene diacid in the solid state. Powder X-ray diffraction and a co-crystallisation are used to solve the structure of the diene and elucidate the stereochemistry of the bicyclobutyl, respectively.

Engineering cocrystal and polymorph architecture via pseudoseeding

Co-reporter:Tomislav Friščić and Leonard R. MacGillivray

Chemical Communications 2009(Issue 7) pp:NaN775-775

Publication Date(Web):2009/01/14

DOI:10.1039/B820120J

We use a cocrystal with components arranged in a 1D hydrogen-bonded chain as a pseudoseed to template the components of a cocrystal that otherwise forms a photoactive 0D assembly to form a photostable 1D chain structure.

Quantitative and regiocontrolled cross-photocycloaddition of the anticancer drug 5-fluorouracil achieved in a cocrystal

Co-reporter:Andrew J. E. Duncan, Roxanne L. Dudovitz, Shawna J. Dudovitz, Jelena Stojaković, S. V. Santhana Mariappan and Leonard R. MacGillivray

Chemical Communications 2016 - vol. 52(Issue 89) pp:NaN13111-13111

Publication Date(Web):2016/10/05

DOI:10.1039/C6CC06570H

We describe a [2+2] cross-photocycloaddition of the anticancer drug 5-fluorouracil in the solid state that proceeds regioselectively and in quantitative yield. The photocycloaddition occurs in a cocrystal with trans-2,2′-bis(pyridyl)ethylene.

Two act as one: unexpected dimers of catechol direct a solid-state [2+2] photodimerization in a six-component hydrogen-bonded assembly

Co-reporter:Giannis S. Papaefstathiou, Andrew J. E. Duncan and Leonard R. MacGillivray

Chemical Communications 2014 - vol. 50(Issue 100) pp:NaN15962-15962

Publication Date(Web):2014/10/31

DOI:10.1039/C4CC07747D

We describe hydrogen-bonded dimers of catechol that act collectively as a single template to direct an intermolecular [2+2] photocycloaddition in the solid state. The directed reactivity involves discrete, six-component hydrogen-bonded assemblies and a photoreaction that occurs stereoselectively and in quantitative yield.

Single-crystal-to-single-crystal direct cross-linking and photopolymerisation of a discrete Ag(I) complex to give a 1D polycyclobutane coordination polymer

Co-reporter:Saikat Dutta, Dejan-Krešimir Bučar, Elizabeth Elacqua and Leonard R. MacGillivray

Chemical Communications 2013 - vol. 49(Issue 11) pp:NaN1066-1066

Publication Date(Web):2012/11/22

DOI:10.1039/C2CC36458A

A discrete dinuclear Ag(I) complex undergoes a single-crystal-to-single-crystal transformation to generate a 1D coordination polymer with a polycyclobutane backbone.

Coding a coordination-driven self-assembly via a hydrogen bond-directed solid-state synthesis: An unexpected chiral tetrahedral capsule

Co-reporter:Tamara D. Hamilton, Dejan-Krešimir Bučar and Leonard R. MacGillivray

Chemical Communications 2007(Issue 16) pp:NaN1604-1604

Publication Date(Web):2007/03/21

DOI:10.1039/B700748E

An achiral ligand, synthesized in the solid state via a coded hydrogen bond-directed organic synthesis, self-assembles with Cu(II) ions to form a chiral tetrahedral capsule that hosts an anion as a guest.

A [2+2] cross-photodimerisation of photostable olefinsvia a three-component cocrystal solid solution

Co-reporter:Dejan-Krešimir Bučar, Arundhuti Sen, S. V. Santhana Mariappan and Leonard R. MacGillivray

Chemical Communications 2012 - vol. 48(Issue 12) pp:NaN1792-1792

Publication Date(Web):2012/01/03

DOI:10.1039/C2CC15453F

A ditopic hydrogen-bond-donor template in the form of resorcinol facilitates a [2+2] cross-photodimerisation of 4-Cl-stilbazole and 4-Me-stilbazole in a rare cocrystal solid solution. A photoreaction does not proceed with the olefins individually or as a solid solution composed solely of the two olefins.

Conformational polymorphism facilitates assignment of trans and cis-conformers of an α-substituted oligothiophene via IR spectroscopy

Co-reporter:Anatoliy N. Sokolov, Joseph C. Sumrak and Leonard R. MacGillivray

Chemical Communications 2010 - vol. 46(Issue 1) pp:NaN84-84

Publication Date(Web):2009/10/19

DOI:10.1039/B915609G

Conformational polymorphism is exploited as a means to assign cis–trans and trans–trans conformations of an oligothiophene backbone using solid-state IR spectroscopy.

Achieving dynamic behaviour and thermal expansion in the organic solid state via co-crystallization

Co-reporter:Kristin M. Hutchins, Ryan H. Groeneman, Eric W. Reinheimer, Dale C. Swenson and Leonard R. MacGillivray

Chemical Science (2010-Present) 2015 - vol. 6(Issue 8) pp:NaN4722-4722

Publication Date(Web):2015/05/26

DOI:10.1039/C5SC00988J

Thermal expansion involves a response of a material to an external stimulus that typically involves an increase in a crystallographic axis (positive thermal expansion (PTE)), although shrinking with applied heat (negative thermal expansion (NTE)) is known in rarer cases. Here, we demonstrate a means to achieve dynamic molecular motion and thermal expansions in organic solids via co-crystallizations. One co-crystal component is known to exhibit dynamic behaviour in the solid state while the second, when varied systematically, affords co-crystals with linear thermal expansion coefficients that range from colossal to nearly zero. Two co-crystals exhibit rare NTE. We expect the approach to guide the design of molecular solids that enable predesigned motion related to thermal expansion processes.

From co-crystals to functional thin films: photolithography using [2+2] photodimerization

Co-reporter:Suman Ghorai, Joseph C. Sumrak, Kristin M. Hutchins, Dejan-Krešimir Bučar, Alexei V. Tivanski and Leonard R. MacGillivray

Chemical Science (2010-Present) 2013 - vol. 4(Issue 11) pp:NaN4308-4308

Publication Date(Web):2013/09/11

DOI:10.1039/C3SC51073E

An approach to form organic thin films that employs multicomponent solids in the form of co-crystals has been developed. The components direct an intermolecular [2+2] photodimerization that we demonstrate exhibits a change in solubility that can be exploited as a negative photoresist for use in photolithography.