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This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. ; The confinement of chemical reactions within small droplets has received much attention in the last few years. This approach has been proved successful for the in-depth study of naturally occurring chemical processes as well as for the synthesis of different sets of nanomaterials with control over their size, shape and properties. Different approaches such as the use of self-contained structures or microfluidic generated droplets have been followed over the years with success. However, novel approaches have emerged during the last years based on the deposition of femtolitre-sized droplets on surfaces using tip-assisted lithographic methods. In this feature article, we review the advances made towards the use of these ultra-small droplets patterned on surfaces as confined nano-reactors. ; M. G. thanks the CSIC for a predoctoral grant (JAEpre). This work was supported by projects MAT2015-70615-R and CTQ2013-41161-R from the Spanish Government and by FEDER funds. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295). ; We acknowledge support by the CSIC Open Access publication initiative through its Unit of Information Resources for Research (URICI). ; Peer reviewed

A bis-catechol ligand connected through an imine bond is used to fabricate switchable coordination polymer particles with pH-tuned spin transition responses. ; This work was supported by the project MAT2012-38318-C03-02 from the Spanish Government and FEDER funds. F. N. thanks Universidad Nacional del Sur for supporting her postdoctoral stay. F. N. thanks the Ministerio de Ciencia e Innovación (MICINN) for a postdoctoral JdC fellowship. The authors also thank ECOSTBio Cost Action. ; Peer Reviewed

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. We have developed a novel approach for grafting coordination polymers, structured as nanoparticles bearing surface reactive carboxylic groups, to amino-functionalized surfaces through a simple carbodiimide-mediated coupling reaction. As a proof-of-concept to validate our approach, and on the quest for novel hybrid interphases with potential technological applications, we have used valence tautomeric nanoparticles exhibiting spin transition at or around room temperature. SEM and AFM characterization reveal that the nanoparticles were organized chiefly into a single monolayer while X-ray photoelectron spectroscopy (XPS) measurements confirm that the nanoparticles retain a temperature-induced electronic redistribution upon surface anchorage. Our results represent an effective approach towards the challenging manufacture of coordination polymers. CPPs immobilization: A generic approach for immobilizing coordination polymer nanoparticles (CPPs) on gold surfaces is reported. The protocol involves covalent bonding between amino-terminated alkyl chains on the gold surface and carboxylic groups on the CPPs surface. The thickness of the nanoparticle monolayer is comparable to the nanoparticle size. The nanoparticles used exhibit valence tautomerism in bulk and keep this property after surface attachment, as corroborated by X-ray photoelectron spectroscopy (XPS) measurements. The results represent an effective approach towards the manufacture of coordination polymers. ; F. N. thanks the Ministerio de Ciencia e Innovación (MICINN) for a postdoctoral JdC fellowship. This work was supported by project MAT2012-38318-C03-02 from the Spanish Government and by FEDER funds. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295). The authors also thank MP1202 Cost Action ; Peer Reviewed

Coordination polymer particles (CPPs) have recently emerged as a new family of nanoparticles. The potential multifunctionality of these nanosystems and the flexibility of their coordination chemistry open new perspectives in different fields, including medicine. This review outlines the most recent advances in this field, from CPP synthesis to their use as smart drug delivery systems, bioimaging probes or a combination of both. © 2013 Elsevier B.V. ; We would like to thank the Spanish Government (grant MAT2012-38318-C03-02 to D.R.-M., JdC grant to F.N. and FPU grant to N.V.-M), Universitat Autònoma de Barcelona (pre-doctoral grant to L.A.-F.) and CSIC (JAEDoc grant to J.S.) for financial support. ; Peer Reviewed

One new lead(II) coordination supramolecular complex (CSC) (1D), [Pb2(L)2(I)4]n, L = C4H6N2 (1-methyl imidazole), has been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on complex 1 showed that Pb2+ ion is 4-coordinated. Topological analysis shows that the complex 1 is 2,3,5C2 net. Finally, the role of reaction time and temperature on the growth and final morphology of the structures obtained by sonochemical irradiation have been studied. ; This work was supported by grant MAT 2015-70615-R from the Spanish Government and by Feder funds. Funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2013-0295). ; Peer reviewed

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.-- et al. ; Synthesis of coordination polymers at femtolitre scales assisted by an AFM tip has become an area of increasing interest due to the astonishing range of implications that derive from it, from gaining basic knowledge of confined reactions in femtolitre droplets to the fabrication of molecular-based devices. However, this field is still in its infancy, a reason why several new basic studies that allow us control over it are highly required. Herein we report the synthesis of [Co(CH3COO)2(μ-4,4′-bpy)] in femtolitre droplets on surfaces and the results are compared with those obtained for the same reaction at different volume scales. ; M. G. thanks the CSIC for a predoctoral grant (JAEpre). This work was supported by project MAT2015-70615-R from the Spanish Government and by FEDER funds. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295). ; We acknowledge the support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI). ; Peer reviewed

Successful nanostructuration approaches developed in the last few years have allowed the preparation of robust valence tautomeric (VT) switchable (micro-/nano-) structures of a variety of dimensions and morphologies. These results are expected to definitely foster the implementation of these materials on hybrid molecular electronic devices but also endorse new applications in other different fields such as sensing, drug delivery or water remediation, among others. ; N. A. V.-M. thanks the Ministerio de Ciencia e Innovación (MICINN) for a predoctoral FPU fellowship. M. G. thanks the CSIC for a predoctoral grant (JAEpre). C. B. thanks the ICN2 and the Severo Ochoa program for his predoctoral grant. This work was supported by projects MAT2015-70615-R and CTQ2015-65439-R from the Spanish Government and by FEDER funds. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295). ; We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI). ; Peer Reviewed

Two new lead(II) coordination polymer complexes (CSCs) (2D), [Pb2(L)2(Br)2]n·H2O (1), [Pb2(HL/)(L/)(H2O)2]n·H2O (2), where L = C6H5NO2 (2-pyridinecarboxylic acid) and L/ = C9H6O6 (1,3,5-tricarboxylic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or microsized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on complexes 1 and 2 shows that Pb2+ ions are 8-coordinated, 7 and 9-coordinated, respectively. Topological analysis shows that the compound 1 and 2 are 4,6L26 and bnn net, respectively. However, neither the shape nor the morphology is maintained, showing the role of sonochemistry to modulate both morphology and dimensions of the resulting crystalline material, independently of whether we have a 2D coordination polymer (CP). Finally, micro structuration of lead(II) bromide oxide and lead(II) oxide have been prepared by calcination of two different lead (II) CPs at 700 °C that were characterized by SEM and XRD. ; This work was supported by grant MAT 2015-70615-R from the Spanish Government and by FEDER funds. Funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2013-0295) University of Milan, University of Sistan and Baluchestan (USB) and Tarbiat Modares University are gratefully acknowledged. ; Peer reviewed

Green light photoactive Ru-based coordination polymer nanoparticles (CPNs), with chemical formula [[Ru(biqbpy)] (bis)](PF) (biqbpy = 6,6-bis[N-(isoquinolyl)-1-amino]-2,2-bipyridine; bis = bis(imidazol-1-yl)-hexane), were obtained through polymerization of the trans-[Ru(biqbpy) (dmso)Cl]Cl complex (Complex 1) and bis bridging ligands. The as-synthesized CPNs (50 ± 12 nm di-ameter) showed high colloidal and chemical stability in physiological solutions. The axial bis(imidazole) ligands coordinated to the ruthenium center were photosubstituted by water upon light irradiation in aqueous medium to generate the aqueous substituted and active ruthenium complexes. The UV-Vis spectral variations observed for the suspension upon irradiation corroborated the photoactivation of the CPNs, while High Performance Liquid Chromatography (HPLC) of irradiated particles in physiological media allowed for the first time precisely quantifying the amount of photoreleased complex from the polymeric material. In vitro studies with A431 and A549 cancer cell lines revealed an 11-fold increased uptake for the nanoparticles compared to the monomeric complex [Ru(biqbpy)(N-methylimidazole) ](PF) (Complex 2). After irradiation (520 nm, 39.3 J/cm), the CPNs yielded up to a two-fold increase in cytotoxicity compared to the same CPNs kept in the dark, indicating a selective effect by light irradiation. Meanwhile, the absence of O production from both nanostructured and monomeric prodrugs concluded that light-induced cell death is not caused by a photodynamic effect but rather by photoactivated chemotherapy. ; his work was supported by grant RTI2018-098027-B-C21 funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe. With the support from "Metalfármacos multifuncionales para el diagnóstico y la terapia" with grant RED2018-102471-T funded by MCIN/AEI/10.13039/501100011033. The ICN2 is funded by the CERCA programme/Generalitat de Catalunya. The ICN2 is supported by the Severo Ochoa Centres of Excellence programme, grant SEV-2017-0706 funded by MCIN/AEI/10.13039/501100011033. J.D. Zhang thanks the BIST PhD Fellowship Programme (This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 754558). NWO is kindly acknowledged for financial support to SB via a VICI grant. COST is kindly acknowledged for stimulating scientific discussion and financial support via the Cost Action CA 17140 "Cancer nanomedicine from the bench to the bedside".

Large blue rectangular crystals of the 2D layered coordination polymer 1 have been obtained. The interest for this complex is two-fold. First, complex 1 is made of 2D layers packing along the (0–11) direction favored by the presence of lattice and coordinated water molecules. And second, nanostructures that could be derived by delamination are potentially suitable for catalytic purposes. Therefore it represents an excellent example to study the role of interlayer solvent molecules on the ultrasound-assisted delamination of functionally-active 2D metal-organic frameworks in water, a field of growing interest. With this aim, ultrasound-assisted delamination of the crystals was optimized with time, leading to stable nanosheet colloidal water suspensions with very homogeneous dimensions. Alternative bottom-up synthesis of related nanocrystals under ultrasound sonication yielded similar shaped crystals with much higher size dispersions. Finally, experimental results evidence that the nanostructures have higher catalytic activities in comparison to their bulk counterparts, due to larger metallic center exposition. These outcomes confirm that the combination of liquid phase exfoliation and a suitable synthetic design of 2D coordination polymers represents a very fruitful approach for the synthesis of functional nanosheets with an enhancement of catalytic active sites, and in general, with boosted functional properties. ; This work was supported by grant RTI2018-098027-B-C21 from the Spanish Government funds and by the European Regional Development Fund (ERDF). The ICN2 is funded by the CERCA programme/Generalitat de Catalunya. The ICN2 is supported by the Severo Ochoa Centres of Excellence programme, funded by the Spanish Research Agency (AEI, grant no. SEV-2017-0706). Noemí Contreras Pereda's project that gave rise to these results received the support of a fellowship from "laCaixa" Foundation (ID 100010434). The fellowship code is LCF/BQ/ES17/11600012. Renhao Dong acknowledgements the financial support from ERC Starting Grant (FC2DMOF, No. 852909) and DFG project (SPP 1928, COORNETs). ; Peer reviewed

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. ; We report a novel hybrid T1/T2 dual MRI contrast agent by the encapsulation of SPIONs (T2 contrast agent) into an iron-based coordination polymer with T1-weighted signal. This new hybrid material presents improved relaxometry and low cytotoxicity, which make it suitable for its use as contrast agent for MRI. ; This work was supported by project MAT2012-38318-C03-02 and MAT2012-35324 and BIO2013-44973-R from the Spanish Government and FEDER funds. F.N. thanks the Ministerio de Ciencia e Innovación (MICINN) for a postdoctoral JdC fellowship and A.L. thanks Ramon y Cajal grant RYC-2010-06082. SM.Y. acknowledges the China Scholarship Council fellowship (201206150053). Authors also thank MP1202 and TD1004 Cost Actions. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, Grant SEV-2013-0295). MR studies were carried out at the joint NMR facility of UAB and CIBER-BBN, Unit 25 of NANBIOSIS, with a 7T horizontal. ; We acknowledge the support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI). ; Peer reviewed

Herein, a new 2-dimensional coordination polymer based on copper (II), {Cu(L)(DMF)}, where L stands for 1,2,4,5-benzenetetracarboxylate (complex 1) is synthesized. Interestingly, we demonstrate that both solvent and sonication are relevant in the top-down fabrication of nanostructures. Water molecules are intercalated in suspended crystals of complex 1 modifying not only the coordination sphere of Cu(II) ions but also the final chemical formula and crystalline structure obtaining {[Cu(L)(HO)]·HO} (complex 2). On the other hand, ultrasound is required to induce the nanostructuration. Remarkably, different morphologies are obtained using different solvents and interconversion from one morphology to another seems to occur upon solvent exchange. Both complexes 1 and 2, as well as the corresponding nanostructures, have been fully characterized by different means such as infrared spectroscopy, x-ray diffraction and microscopy. ; This work was supported by grant RTI2018-098027-B-C21 from the Spanish Government funds and by the European Regional Development Fund (ERDF). The ICN2 is funded by the CERCA programme / Generalitat de Catalunya. The ICN2 is supported by the Severo Ochoa Centres of Excellence program, funded by the Spanish Research Agency (AEI, grant no. SEV-2017-0706). Noemí Contreras Pereda's project that gave rise to these results received the support of a fellowship from "laCaixa" Foundation (ID 100010434). The fellowship code is LCF/BQ/ES17/11600012.

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. ; The idea of developing magnetic molecular materials into real functional electronic devices with low-cost and scalable techniques appeared with the emergence of the field several years ago. Today, even though great advances have been done with this aim, the promise of a functional device working at the micro-/nanoscale and at room temperature has unfortunately not completely materialized yet, as their use still strongly depends on the fabrication methodology of a robust device that can be handled and integrated without compromising their functionality. Here we propose the use of polymeric matrices as a platform for the development of such robust switchable structures exhibiting reproducible results independently of the dimension-from macro to micro-/nanoscale-and morphology-from thin-films to nanoparticles and nanoimprinted motives-while allowing to induce an irreversible hysteresis, reminiscent of a non-volatile memory, by synchronization with the polymer phase transition. ; This work was supported by project MAT2012-38318-C03-02. F.N. thanks the MICINN for a JdC fellowship. N.V. thanks the Spanish government for her Ph.D. Fellowship support. ; Peer Reviewed

Development of novel 2D materials with singular and thrilling properties has aroused large interest due to the novel unexpected applications that can be derived from there. In this sense, coordination polymers (CPs) have appeared as matching candidates thanks to their rational chemical design and the added-value properties given by the presence of metal ions. This is the case of switchable spin-crossover systems that have been proposed as excellent candidates for data storage or sensing, among others. Here we report the delamination of crystals of the 2D spin-crossover (SCO) {[Fe(L1)2](ClO4)2}∝ (1) CP by liquid-phase exfoliation (LPE) in water. The application of this top-down technique results in the formation of flakes with controlled thicknesses, down to 1–2 nm thick (mostly mono- and bilayer), that retain the chemical composition and SCO interconversion of the bulk material. Moreover, these flakes can be handled as stable colloidal dispersions for many days. This allows for a controlled transfer to solid substrates and the formation of thermochromic polymeric films as a proof-of-concept of device. These first results will definitely open new venues and opportunities for the investigation and future integration of these original switchable 2D materials in devices. ; This work was supported by projects MAT2015-70615-R, CTQ2015-65439-R, and FIS2015-64886-C5-3-P from the Spanish Government funds and by European Regional Development Fund (ERDF). Funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant SEV-2013-0295). Funded by the project 2014-SGR-301 (Generalitat de Catalunya). This work was supported by the Fonds National de la Recherche Scientifique-FNRS (PDR T.0102.15) and COST actions CM1305 and CA15128. M. M. D is a chargé de recherches from the F.R.S.-FNRS. S.S.-G. acknowledges the support from MINECO BES-2015-071492 grant. R.R. and P.O. acknowledge support from EU H2020-EINFRA-5-2015 MaX Center of Excellence (Grant 676598). ; Peer reviewed