Arnaud Grosjean

Atomic resolution of structural changes in elastic crystals of copper (II) acetylacetonate

Single crystals are typically brittle, inelastic materials. Such mechanical responses limit their use in practical applications, particularly in flexible electronics and optical devices. Here we describe single crystals of a well-known coordination compound-copper(II) acetylacetonate-that are flexible enough to be reversibly tied into a knot. Mechanical measurements indicate that the crystals exhibit an elasticity similar to that of soft materials such as nylon, and thus display properties normally associated with both hard and soft matter. Using microfocused synchrotron radiation, we mapped the changes in crystal structure that occur on bending, and determined the mechanism that allows this flexibility with atomic precision. We show that, under strain, the molecules in the crystal reversibly rotate, and thus reorganize to allow the mechanical compression and expansion required for elasticity and still maintain the integrity of the crystal structure.

A three-dimensional cubic halogen-bonded network

The rational, deliberate design of supramolecular architectures is of great importance for the discovery of complex materials. A three-dimensional cubic halogen-bonded network has been prepared by combination of an octahedral metal-containing halogen bond acceptor and a linear ditopic donor. This material displays α-Po pcu topology and is seven-fold interpenetrated. This is the first neutral, metal-containing three-dimensional halogen-bonded network to be reported.

Zero in-Plane Thermal Expansion in Guest-Tunable 2D Coordination Polymers

Zero in-plane thermal expansion (TE) in a two-dimensional (2D) coordination polymer is demonstrated. The combination of components that expand and those that shrink into zigzag layers results in no net area change in the 2D materials with temperature. Single crystals of [Mn(salen)]2[Mn(N)(CN)4(guest)] (salen = N,N-ethylenebis(salicylideneaminato), guest = MeOH and MeCN) were prepared, and variable-temperature single-crystal X-ray structural analyses demonstrated that these compounds exhibited both anisotropic positive and negative thermal expansion depending on the guest species. The TE behavior results from distortions of the octahedral coordination geometry of [Mn(salen)]+ units in the zigzag layers. When both guests MeOH and MeCN were incorporated into one material, [Mn(salen)]2[Mn(N)(CN)4(MeOH)0.25(MeCN)0.75], zero in-plane TE resulted in a range of temperature between 380 and 440 K.

Positive and Negative Two-Dimensional Thermal Expansion via Relaxation of Node Distortions

The ability to tune physical properties is attractive for the development of new materials for myriad applications. Understanding and controlling the structural dynamics in complicated network structures like coordination polymers (CPs) is particularly challenging. We report a series of two-dimensional CPs [Mn(salen)]2[M(CN)4]· xH2O (M = Pt (1), PtI2 (2), and MnN (3)) incorporating zigzag cyano-network layers that display composition-dependent anisotropic thermal expansion properties. Variable-temperature single-crystal X-ray structural analyses demonstrated that the thermal expansion behavior is caused by double structural distortions involving [Mn(salen)]+ units incorporated into the zigzag layers. Thermal relaxations produce structural transformations resulting in positive thermal expansion for 2·H2O and negative thermal expansion for 3. In the case of 1·H2O, the relaxation does not occur and zero thermal expansion results in the plane between 200 to 380 K. The present study proposes a new strategy based on structural distortions in coordination networks to control thermal responsivities of frameworks.

Elastically Flexible Crystals have Disparate Mechanisms of Molecular Movement Induced by Strain and Heat

Elastically flexible crystals form an emerging class of materials that exhibit a range of notable properties. The mechanism of thermal expansion in flexible crystals of bis(acetylacetonato)copper(II) is compared with the mechanism of molecular motion induced by bending and it is demonstrated that the two mechanisms are distinct. Upon bending, individual molecules within the crystal structure reversibly rotate, while thermal expansion results predominantly in an increase in intermolecular separations with only minor changes to molecular orientation through rotation.

CCDC 1529014: Experimental Crystal Structure Determination

Related Article: Anna Worthy, Arnaud Grosjean, Michael C. Pfrunder, Yanan Xu, Cheng Yan, Grant Edwards, Jack K. Clegg, John C. McMurtrie|2017|Nature Chemistry|||doi:10.1038/nchem.2848

CCDC 1529012: Experimental Crystal Structure Determination

Related Article: Anna Worthy, Arnaud Grosjean, Michael C. Pfrunder, Yanan Xu, Cheng Yan, Grant Edwards, Jack K. Clegg, John C. McMurtrie|2017|Nature Chemistry|||doi:10.1038/nchem.2848

CCDC 1529021: Experimental Crystal Structure Determination

Related Article: Anna Worthy, Arnaud Grosjean, Michael C. Pfrunder, Yanan Xu, Cheng Yan, Grant Edwards, Jack K. Clegg, John C. McMurtrie|2017|Nature Chemistry|10|65|doi:10.1038/nchem.2848

CCDC 1529040: Experimental Crystal Structure Determination

Related Article: Anna Worthy, Arnaud Grosjean, Michael C. Pfrunder, Yanan Xu, Cheng Yan, Grant Edwards, Jack K. Clegg, John C. McMurtrie|2017|Nature Chemistry|10|65|doi:10.1038/nchem.2848