Growth of lamellar Hofmann clathrate films by sequential ligand exchange reactions: assembling a coordination solid one layer at a time

Bell, Christine M.; Arendt, M.; Gomez, L.; Schmehl, Russell H.

doi:10.1021/ja00097a058

Cited by 83 publications

(50 citation statements)

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“…Little is known about PCP or MOF crystallization mechanisms for solvothermal, [7] or surface controlled growth. [8] More experimental and theoretical studies are required to fully understand the surface chemistry of PCPs and MOFs at the liquid/solid interface, as we have discussed elsewhere.…”

Section: Resultsmentioning

confidence: 99%

“…It is noteworthy that as early as in 1993, Mallouk and co-workers reported the LbL growth of self-assembled Hofmann clathrate multilayers of [Ni-A C H T U N G T R E N N U N G (bipy)Pt(CN) 4 ] (bipy = 4,4'-bipyridine) type by sequential ligand exchange reactions at the surface, although without proof of crystalline order. [7] Clearly, layer-based PCPs (Figure 2) are structurally more or less related to the Hofmann clathrates and should be particularly suited for LbL growth, since the pronounced anisotropy of this class of PCPs is highly compatible with the boundary conditions dictated by a nucleating, two-dimensional substrate. However, only very few such cases have been reported so far, including [Fe(pz){Pt(CN) 4 }] (pz = pyrazin) [8] and [ZnA C H T U N G T R E N N U N G (bdc)A C H T U N G T R E N N U N G (bipy) 0.5 ] (MOF-508; bdc = 1,4-benzenedicarboxylic acid).…”

Section: A C H T U N G T R E N N U N G (Btc) 2 -A C H T U N G T R E Nmentioning

confidence: 99%

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Liquid‐Phase Epitaxy of Multicomponent Layer‐Based Porous Coordination Polymer Thin Films of [M(L)(P)0.5] Type: Importance of Deposition Sequence on the Oriented Growth

Zacher¹,

Yusenko²,

Bétard³

et al. 2011

Chemistry A European J

164

183

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The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)(0.5)] (M: Cu(2+), Zn(2+); L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars.

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Section: Resultsmentioning

confidence: 99%

Section: A C H T U N G T R E N N U N G (Btc) 2 -A C H T U N G T R E Nmentioning

confidence: 99%

Liquid‐Phase Epitaxy of Multicomponent Layer‐Based Porous Coordination Polymer Thin Films of [M(L)(P)0.5] Type: Importance of Deposition Sequence on the Oriented Growth

Zacher¹,

Yusenko²,

Bétard³

et al. 2011

Chemistry A European J

164

183

View full text Add to dashboard Cite

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“…This finding seems rational for us, taking into account a 3D-growth scheme from a number of surface nucleation sites, but it is in significant disagreement with the report of Mallouk and co-workers on the growth of Ni(4,4′-bipyridine)[Pt(CN) 4 ] coordination polymers. [16] One should also be aware that in contrast to the idealized layer-by-layer deposition scheme of polyionic organic compounds, [7] the assembly of 1 involves not only adsorption steps but also desorption and re-adsorption accompanied by the formation of crystallites. As suggested in the literature, [17] we have tried to minimize such phenomena by keeping the dipping times as short as possible.…”

mentioning

confidence: 99%

A Combined Top‐Down/Bottom‐Up Approach for the Nanoscale Patterning of Spin‐Crossover Coordination Polymers

Molnár¹,

Cobo²,

Real³

et al. 2007

Advanced Materials

207

121

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Molecular spin-crossover complexes of 3d 4 -3d 7 transitionmetal ions have been the focus of many researchers' work because of their fascinating properties associated with the bistability of their electronic states (high spin (HS) or low spin (LS)). [1] Although the origin of the spin-crossover phenomenon is purely molecular, the macroscopic behavior of these systems in the solid state is strongly determined by the interactions, of mainly elastic origin, between the transition-metal ions.[2]Recently, remarkable progress has been made in the area of spin-crossover complexes with infinite one-, two-, or three-dimensional (1D, 2D, 3D) networks, the so-called coordination polymers.[3] The purpose of this approach was the enhancement and fine tuning of cooperative properties by the strong covalent links between the metallic centers in the polymers.[4]Indeed, a number of highly cooperative polymer systems have been reported in the recent literature that display hysteretic behavior (thermal and piezo), in some cases even at room temperature. In addition to this, we have recently demonstrated that 3D coordination polymers represent an attractive platform for growth of surface thin films with spin-crossover properties. [5] In fact, the 3D network structure allows the sequential assembly, via stepwise adsorption reactions, of multilayer films based entirely on intra-and interlayer coordination bonds. These films have opened up possibilities for investigating size-reduction effects, optical and dielectric properties, and device applications of spin-crossover materials.[6]A further step in this direction is the generation of microand nanometer-sized lateral patterns. In fact, the multilayer sequential assembly (MSA) process (also called directed assembly or layer-by-layer assembly in the literature [7] ) has become increasingly popular not only for fabricating thin films but also many efforts have been devoted to generating distinct patterns of the multilayer films. Various lithographic and nonlithographic methods-such as deposition on chemically patterned surfaces, inkjet printing, lift-off processes, etching, direct photopatterning, and microcontact printing-have been explored with this aim.[8] Each method has, of course, different merits, but the lift-off process remains an industry standard owing to its simplicity and reliability. Furthermore, when combined with electron-beam lithography (EBL), it allows patterns to be obtained in a wide size range down to the sub-10 nm limit, [9] and the alignment of the patterns is also possible with respect to structures that may already exist on the substrate. In this Communication, we report on a process for nanoand microscale assembly of the 3D spin-crossover coordination polymer Fe(pyrazine)[Pt(CN) 4 ] (1) (Scheme 1) by using a combination of top-down (lift-off) and bottom-up (MSA) methods. We call attention to the 3D polymer nature of this system, which is the key aspect for 1) obtaining room-temperature hysteresis, 2) assembling multilayers, and 3) performing COMMUNICATION

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“…3 Forces between the layers are primarily electrostatic interaction and covalent bonding, but they can also involve hydrogen bonding, p-p interaction, and coordination bonding of monomeric or polymeric ligands with transition metal ions. 4,5 A relatively weaker charge transfer (CT) interaction as the driving force of the LBL self-assembly was recently used to prepare ultrathin films. [6][7][8][9] Incorporation of noble metal nanoparticles into the LBL films consisting of pconjugated conducting polymers presents promising materials for both catalytic applications, in which conducting polymer beds with catalyst nanoparticles gathering close to the film surfaces provide optimum catalytic situations, and nanotechnological fabrication.…”

Section: Introductionmentioning

confidence: 99%

Layer‐by‐layer films based on charge transfer interaction of ϕ‐conjugated poly(dithiafulvene) and incorporation of gold nanoparticles into the films

Wang

Naka

Wang

et al. 2006

J of Applied Polymer Sci

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Layer-by-layer (LBL) self-assembled ultrathin films were prepared via consecutively alternating immersion of substrates into solutions of electron donor, poly(dithiafulvene) (PDF), and electron acceptor, poly(hexanyl viologen) (6-VP). The charge transfer (CT) interaction formed at solid-liquid interfaces between the backbones of the electron acceptor and donor polymers was the driving force of the alternative deposition. The sandwich heterostructure of the LBL film led to electrical anisotropy in the directions parallel and perpendicular to the film surfaces. Incorporation of gold nanoparticles into the LBL films was investigated by reducing gold ions with the PDF layers already deposited on the film surfaces, or depositing PDFprotected gold colloidal solution as the electron donor layers directly. The influence of the gold nanoparticles on the electrical anisotropy of the LBL films was also illustrated in this research.

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Growth of lamellar Hofmann clathrate films by sequential ligand exchange reactions: assembling a coordination solid one layer at a time

Cited by 83 publications

References 0 publications

Liquid‐Phase Epitaxy of Multicomponent Layer‐Based Porous Coordination Polymer Thin Films of [M(L)(P)0.5] Type: Importance of Deposition Sequence on the Oriented Growth

Liquid‐Phase Epitaxy of Multicomponent Layer‐Based Porous Coordination Polymer Thin Films of [M(L)(P)0.5] Type: Importance of Deposition Sequence on the Oriented Growth

A Combined Top‐Down/Bottom‐Up Approach for the Nanoscale Patterning of Spin‐Crossover Coordination Polymers

Layer‐by‐layer films based on charge transfer interaction of ϕ‐conjugated poly(dithiafulvene) and incorporation of gold nanoparticles into the films

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