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Introduction: Despite a decline in Sudden Unexpected Death in Infancy in the UK since 2004, inequalities have widened with higher rates among families from deprived backgrounds and those known to child protection services. Almost all cases involve parents who had engaged in unsafe sleeping practices despite awareness of safer sleeping advice. Objective: To understand the perspectives surrounding safer sleep of families supported by statutory child protection agencies, and use behavior change theory to inform how approaches to providing safer sleep advice to these families may be modified. Participants and setting: We interviewed 14 mothers, 2 fathers and one grandmother, who had recent contact with child protection services in northeast England. Methods: In-depth, semi-structured interviews, with purposive sampling. The COM-B model (Capability, Opportunity, and Motivation) structured our analysis. Results: Parents described how anxiety, sleep deprivation, settling infants, illness, and a desire to bond with infants influence their decision making about sleep. Parents valued credible, trusted sources and understanding how safer sleep practices protect infants. Responses to questions about 'out of routine' situations suggested social pressures surrounding routines and 'good parenting' may preclude parents from acknowledging risks and planning for these situations. Conclusion: Open conversations tailored to the needs of families, focused upon understanding why and when parent(s) do or do not follow safer sleep guidance seem a promising way of promoting safer sleep practices. Safer sleep discussions with these families are likely to be best delivered as part of wider infant care by professionals who have an established and continuing trusting relationship with parents. While advice and information should be provided by any professional in contact with the family with the necessary expertise, sensitive conversations around sleeping practices, particularly co-sleeping, may be more easily facilitated by professionals where the statutory responsibility for safeguarding is less apparent. [ABSTRACT FROM AUTHOR]

Introduction: Children exposed to parental intimate partner violence and abuse, mental illness, and substance use experience a range of problems which may persist into adulthood. These risks often co-occur and interact with structural factors such as poverty. Despite increasing evidence, it remains unclear how best to improve outcomes for children and families experiencing these adversities and address the complex issues they face. Aims and Methods: Systematic review of systematic reviews. We searched international literature databases for systematic reviews, from inception to 2021, to provide an evidence overview of the range and effectiveness of interventions to support children and families where these parental risk factors had been identified. Results: Sixty-two systematic reviews were included. The majority (n = 59) focused on interventions designed to address single risk factors. Reviews mostly focused on parental mental health (n = 38) and included psychological interventions or parenting-training for mothers. Only two reviews assessed interventions to address all three risk factors in combination and assessed structural interventions. Evidence indicates that families affected by parental mental health problems may be best served by integrated interventions combining therapeutic interventions for parents with parent skills training. Upstream interventions such as income supplementation and welfare reform were demonstrated to reduce the impacts of family adversity. Conclusion: Most intervention approaches focus on mitigating individual psychological harms and seek to address risk factors in isolation, which presents potentially significant gaps in intervention evidence. These interventions may not address the cumulative impacts of co-occurring risks, or social factors that may compound adversities. [ABSTRACT FROM AUTHOR]

The parental risk factors of mental health problems, substance use, and domestic violence and abuse each individually negatively impacts children's health and developmental outcomes. Few studies have considered the lived experience and support needs of parents and children in the real-world situation where these common risks cluster. This study explores parents' and young people's lived experiences of the clustering of parental mental health problems, parental substance use, and domestic violence and abuse. Semi-structured interviews were conducted with 18 mothers, 6 fathers, and 7 young people with experiences of these parental risk factors. Transcribed interviews were analysed using reflexive thematic analysis. Four themes were developed, 1) cumulative adversity, 2) the impact of syndemic risk, 3) families navigating risk, and 4) family support. Parents and young people described family situations of stress wherein they experienced cumulative impact of multiple parental risk factors. Parents sought to navigate stressors and parent in positive ways under challenging conditions, often impeded by their own childhood trauma and diminished confidence. Parents and young people spoke of the need for, and benefits of having, support; both as a family and as individuals, to successfully address this trio of parental risks and the related impact. This study highlights the high level of stress families experience and the efforts they go to mitigate risk. Services and interventions need to reflect the complexity of multiple needs and consider both the whole family and individuals when providing support. [ABSTRACT FROM AUTHOR]

Patient involvement in their own treatment can enable those with wounds in the community to play an active role in the management of their condition by, for example, completing dressing changes between health professional visits. The original primary study was undertaken to assess the clinical effectiveness of Zetuvit Plus Silicone Border (ZPSB) on exudate management. This retrospective sub-group analysis is aimed to demonstrate the effectiveness of a superabsorbent polymer (SAP) dressing (ZPSB) in enabling patients or their carers to undertake unsupervised dressing changes on their own. ZPSB was found to be clinically effective in this subgroup of patients, while also having additional features that enabled the patient to self-care. Overall, ZPSB enabled the patient to be part of their treatment plan and play an active role in the care of their wounds, thereby promoting self-care. This had a positive effect on nursing time saving and patient satisfaction. [ABSTRACT FROM AUTHOR]

Non-healing wounds are a significant burden to healthcare systems, where it is estimated that 4-5% of the adult population has a problem wound at any one time (Guest et al, 2017). It is suggested that infection is the most frequent complication in non-healing wounds where it can prolong patient treatment times and increase resource use (Gottrup et al, 2013). Wound infection develops as a result of an imbalance between the patient’s immune system and the conditions in the wound, which subsequently can promote bacterial proliferation (Wounds UK, 2013). It can impact on the patient by delaying wound healing, increasing the risk of amputation and life-threatening conditions, and reducing quality of life. The use of antibiotics to treat wound infections has decreased due to the increased risk of antibiotic resistance (Swanson et al, 2014). As a result alternative strategies for preventing and managing wound infection have been adopted, including wound debridement and the use of topical antiseptic/antimicrobial agents. [ABSTRACT FROM AUTHOR]

This article examines the use of Mepîtel® One, a wound contact layer that promotes wound healing by using the clinical benefits of Safetac® technology. A wide range of clinical evidence shows that dressings with Safetac prevent trauma, minimise wound pain and associated psychological stress, while facilitating undisturbed wound healing. Mepitel One has been developed as a highly transparent wound contact layer with Safetac on the wound contact surface alone; this makes it easy to apply without sticking to gloves, and allows it to be used with a choice of secondary dressings. The dressing can stay in place for up to 14 days and allows examination of the wound without removal. The clinical evidence reviewed here shows that Mepitel One is a versatile option for use on a wide range of wound types to promote undisturbed healing and minimise pain at dressing changes. [ABSTRACT FROM AUTHOR]

This article examines the use of Mepîtel® One, a wound contact layer that promotes wound healing by using the clinical benefits of Safetac® technology. A wide range of clinical evidence shows that dressings with Safetac prevent trauma, minimise wound pain and associated psychological stress, while facilitating undisturbed wound healing. Mepitel One has been developed as a highly transparent wound contact layer with Safetac on the wound contact surface alone; this makes it easy to apply without sticking to gloves, and allows it to be used with a choice of secondary dressings. The dressing can stay in place for up to 14 days and allows examination of the wound without removal. The clinical evidence reviewed here shows that Mepitel One is a versatile option for use on a wide range of wound types to promote undisturbed healing and minimise pain at dressing changes. [ABSTRACT FROM AUTHOR]

Chronic wounds come in all shapes and sizes and may be associated with co-morbidities that have a direct impact upon healing and the quality of life of patients, their families, carers, and even co-workers. Cosmetic appearance is important to both genders but especially so to female patients and unsightly wounds that are difficult to hide cause extreme problems that may have psychological implications. In addition to the effect that they have on patients, these wounds are associated with considerable resource requirements, which impact heavily on the already burdened NHS. This article presents three case studies of patients with chronic wounds that have shown a positive response, in terms of healing and impact upon the patient's quality of life, to an advanced wound care product -- Xelma®. [ABSTRACT FROM AUTHOR]

This article examines the role of a unique dressing--Mepilex® Ag--that incorporates the rapid and sustained antimicrobial action of ionic silver with the benefits of Safetac® soft silicone adhesive technology. The combined attributes of each component of this dressing allow both the control of pain and infection to be achieved simultaneously. This dual approach to the management of wounds is of significance since the evidence suggests that wound infection and the release of pro-inflammatory modulators result in both local pain and delayed healing. In this respect the control and treatment of pain is as important as the treatment of infection itself. A review of the clinical evidence relating to Safetac technology clearly demonstrates that it can be used to prevent dressing-related trauma, minimize pain at dressing change, and control exudate when used on a wide range of wound types and skin injuries. In combination with silver, this technology has been shown in in-vitro studies to have an almost instant and sustainable antimicrobial effect on a broad range of pathogens associated with delayed healing. Finally, in small clinical and case studies, Mepilex Ag has been shown to control wound bioburden and improve healing rates. [ABSTRACT FROM AUTHOR]

As a number of consensus and position documents have made clear, wound pain is an issue that all nurses involved in wound care should take seriously. Based on the 'Heal not hurt' initiative supported by Molnlycke, a wound assessment tool has been adopted by East Riding of Yorkshire PCT. This article gives an overview of the documentation and argues that thorough assessment is essential in wound care and proper documentation is the key to successful clinical outcomes. [ABSTRACT FROM AUTHOR]

As a number of consensus and position documents have made clear, wound pain is an issue that all nurses involved in wound care should take seriously. Based on the ‘Heal not hurt’ initiative supported by Molnlycke, a wound assessment tool has been adopted by East Riding of Yorkshire PCT. This article gives an overview of the documentation and argues that thorough assessment is essential in wound care and proper documentation is the key to successful clinical outcomes. [ABSTRACT FROM AUTHOR]

The complexes [Fe(L1R)2]X2 (L1R = 2,6-bis-{3-iso-propylpyrazol-1-yl}pyridine[L1Pri], X−=BF4− or PF6−; L1R = 2,6-bis-{3-phenylpyrazol-1-yl}pyridine [L1Ph], X−=BF4−) are high-spin between 5 and 300 K in the solid, and between 180 and 300 K in acetone solution. In contrast, [Fe(L1Mes)2]X2 (L1Mes = 2,6-bis-{3-[2,4,6-trimethylphenyl]pyrazol-1-yl}pyridine, X−=BF4− or PF6−) are fully low-spin at 300 K in the solid and solution phases. This shows that the spin state of the Fe ion in these compounds depends on the inductive properties of the ligand 3,3″-substituents only, as long as those substituents are aromatic. [Copyright &y& Elsevier]

As a number of consensus and position documents have made clear, wound pain is an issue that all nurses involved in wound care should take seriously. Based on the 'Heal not Hurt'™ initiative supported by Molnlycke, a wound assessment tool has been adopted by East Riding of Yorkshire PCT. This article gives an overview of the documentation and argues that thorough assessment is essential in wound care and proper documentation is the key to successful clinical outcomes. [ABSTRACT FROM AUTHOR]

Rates of sudden unexpected death in infancy have been found to occur disproportionately amongst families living in the most deprived neighbourhoods. This suggests that standard safer sleep messaging may not be effective for this population and that research is required to identify ways of working that are better associated with behavioural change in parents with children at increased risk of SUDI. In this study, we aimed to explore the behavioural change components and mechanisms of action of safer sleep interventions for families with children at increased risk of SUDI. We conducted an analysis of the literature on safer sleep interventions using the COM‐B model, Theoretical Domains Framework and Behavioural Change Technique Taxonomy. All interventions targeted parents' capability; 15 interventions targeted parents' opportunity; and six interventions targeted parents' motivation to engage in safer sleep practices. Nineteen behavioural change techniques were identified. The focus of practitioners may need to shift from solely the delivery of safer sleep information towards working with parents to understand their capability, opportunity and, in particular, motivation to engage in safer sleep practices, identified as being a key driver of behaviour in this population. [ABSTRACT FROM AUTHOR]

Background: Adolescence is characterized by identity formation, exploration and initiation of intimate relationships. Much of this occurs at school, making schools key sites of sexual harassment. Schools often lack awareness and understanding of the issue, and UK research on the topic is scarce. We explored prevalence and perceptions of sexual harassment in a school-based mixed-methods study of 13–17 year-old Scottish adolescents. Methods: A student survey (N = 638) assessed past 3-months school-based victimization and perpetration prevalence via 17 behavioral items based on the most commonly used school-based sexual harassment measure ('Hostile Hallways'). Eighteen focus groups (N = 119 students) explored which of 10 behaviors were perceived as harassing/unacceptable and why. Results: Two-thirds reported any victimization: 64.7% 'visual/verbal' (e.g. sexual jokes) and 34.3% 'contact/personally-invasive' behaviors (e.g. sexual touching; most of whom also reported experiencing visual/verbal types) in the past 3-months. Data suggested a gateway effect, such that contact/personally-invasive behaviors are more likely to be reported by those also reporting more common visual/verbal behaviors. Some survey participants reported being unsure about whether they had experienced certain behaviors; and in focus groups, participants expressed uncertainty regarding the acceptability of most behaviors. Ambiguities centered on behavioral context and enactment including: degree of pressure, persistence and physicality; degree of familiarity between the instigator-recipient; and perception of the instigator's intent. In attempting to resolve ambiguities, students applied normative schemas underpinned by rights (to dignity, respect and equality) and 'knowingness', usually engendered by friendship. Conclusions: Our study confirms school-based sexual harassment is common but also finds significant nuance in the ways in which students distinguish between acceptable and harassing. School-based strategies to tackle sexual harassment must engage with this complexity. [ABSTRACT FROM AUTHOR]

Abstract: Reaction of 2 equiv of the sodium salt of ethyl pyrazole-4-carboxylate, with 1 equiv of 2,6-dibromopyridine, in diglyme at 130°C for 5days yields 2,6-di[4-(ethylcarboxy)pyrazol-1-yl]pyridine (L1), with 2-bromo-6-[4-(ethylcarboxy)pyrazol-1-yl]pyridine (L2) as a significant byproduct. Reduction of L1 with excess NaBH4 in thf affords 2,6-di[4-(hydroxymethyl)pyrazol-1-yl]pyridine (L3) in low yield. The crystalline complex [Fe(L1)2][BF4]2 ·2CF3CH2OH is low-spin at 150K, while bulk samples with this formula are approximately 10% high-spin and 90% low-spin at room temperature. This ratio does not vary significantly on cooling from its magnetic susceptibility, suggesting that the material might be contaminated by a second, minor high-spin phase. Single crystals of [Fe(L3)2][BF4]2·1.4CH3CN have a mixed spin-state population, with the low-spin state predominating at 150K. The [Fe(L3)2(BF4)]+ moieties in the lattice associate into 1-D chains through intermolecular O–H⋯O and O–H⋯F hydrogen bonding. Bulk samples of [Fe(L3)2][BF4]2 ·H2O are fully low-spin below 200K, but the magnetic data imply the onset of a gradual thermal spin-transition centred above room temperature. DSC and TGA measurements imply that this transition is centred at 322K, and involves loss of lattice water. Both complexes undergo spin-crossover in (CD3)2CO solution, with transition midpoints near 250K. [Copyright &y& Elsevier]

The selective esterifications of L-malic, L-tartaric and citric acids with tetramethoxysilane Si(OMe)4, in methanol (MeOH) have been demonstrated for the first time. The interactions between these acids and Si(OMe)4, and also between oxalic acid and Si(OMe)4, were investigated using 1H, 13C and 29Si solution phase NMR, and electrospray mass spectrometry (ES-MS). Si(OMe)4 acts as a catalyst/reagent in the selective esterification of simple 2-hydroxycarboxylic acids (2HOAs), but with the di- and tri-carboxylic acids more complex selectivities are observed: the esterification of oxalic acid proceeds slower than in MeOH alone, L-malic acid is selectively esterified ∼1000 times faster at the 2-hydroxy acid, L-tartaric acid is esterified ∼1000 times faster to the mono- and diester, while citric acid is selectively methylated at the terminal (3-hydroxycarboxyl) groups ∼1000 times faster than in the absence of Si(OMe)4. Esterification is associated with the condensation of silane units to form oligomers. A mechanism is proposed in which 2HOAs attach to silicon via the alkoxy group and carboxyl groups to form various reactive cyclic intermediates. These intermediates may lead to accelerated esterification via nucleophilic attack of MeOH at the ligated carboxyl group, while a separate reaction pathway leads to condensation of silicon centres leading to oligosilanes. The mechanism has implications for the use of 2HOAs as templates in sol-gel silica preparation. [ABSTRACT FROM AUTHOR]

The syntheses of [FeL][BF4]2·H2O, [FeL][ClO4]2·H2O, [FeL][NO3]2·CH3NO2 and [FeL][CF3SO3]2 (L = tris(4-{pyrazol-3-yl}-3-aza-3-butenyl)amine) are described. The isostructural BF4 − and ClO4 − salts are high-spin between 5-300 K, while the other two compounds are high-spin at room temperature but undergo gradual high→low spin transitions upon cooling. For [FeL][NO3]2 this transition is centred at 139 K and proceeds to near-completeness, while for [FeL][CF3SO3]2 it is centred at 144 K and only proceeds to 50% conversion. The CF3SO3 − salt also undergoes spin-crossover centred at 200 K in (CD3)2CO solution, and exhibits dynamic inversion of its helical ligand conformation. All these compounds except the triflate salt have been crystallographically characterised, and show capped trigonal antiprismatic [6 + 1] coordination geometries. The NO3 − and CF3SO3 − salts undergo quantitative conversion to trapped, high-spin excited states upon irradiation with a green laser at 10 K (the LIESST effect; LIESST = Light-Induced Excited Spin State Trapping). The thermal stabilities of their LIESST excited states (T(LIESST) = 80-82 K) resemble those found for iron(II) complexes of bidentate N-heterocyclic ligands. Hence, the LIESST properties of [FeL]2+ are those of a complex of three rigid bidentate domains linked by a flexible spacer, rather than of a single encapsulating podand. [ABSTRACT FROM AUTHOR]

Reaction of hydrated Zn[NO3]2 or Zn[BF4]2 with four or more equivalents of 3{5}-tert-butylpyrazole (LtBu) yields [Zn(LtBu)4]X2 (X- = NO3- or BF4-). The nitrate complex contains C2-symmetric four-coordinate zinc(II) centers with a slightly flattened tetrahedral geometry, and each nitrate anion hydrogen bonds to two pyrazole N-H groups. Similar reactions with Zn[ClO4]2 or ZnCl2 in the presence of 2 equiv of AgPF6 or AgSbF6 yield instead [{Zn(LtBu)4}-(LtBu)4][ClO4]2 and [{Zn(LtBu)4}(LtBu)2]Y2 (Y = PF6- or SbF6-). Crystals of [{Zn(LtBu)4}(LtBu)4][ClO4]2 are composed of discrete [{Zn(LtBu)4}(LtBu)4]2+ supramolecules that are formed from N-H⋯N hydrogen bonding between zinc- bound and uncoordinated pyrazole rings. The [{Zn(LtBu)4}(LtBu)4]2+ moieties are linked into planar 44 nets by hydrogen bonding to bridging ClO4- anions. The ClO4- ions are almost perfectly encapsulated in near-spherical cavities of approximate dimensions 5.0 × 5.0 × 4.5 Åthat are formed by two interlocked supramolecular dications. Similarly, [{Zn(LtBu4)4}(LtBu)2][PF6]2 crystallizes as discrete supramolecules in the crystal with the PF6- anions occupying a shallow bowl-shaped cavity on the surface of the complex that is formed by two zinc-bound and one uncoordinated pyrazole ligands. ¹H NMR and IR studies of [{Zn(LtBu)4}(LtBu)4][ClO4]2 in CD2Cl2 imply that the second-sphere LtBu ligands dissociate from the [Zn(LtBu)4]2+ center in this solvent and that free and metal-bound LtBu are in rapid chemical exchange. [ABSTRACT FROM AUTHOR]

Abstract: Reaction of terBuNC with anti-B18H22 in CH2ClCH2Cl gives [7-{(terBuNHCH){terBuNHC(CN)}CH2}-anti-B18H20] in which a reductive oligomerisation of the terBuNC residues has given the complex polynitrogen base {(terBuNHCH){terBuNHC(CN)}CH2:}, formally as a zwitterionic carbene attached to the macropolyhedral {B18H20} cluster. [Copyright &y& Elsevier]

The complex [ZnBr2L ¹] (L ¹ = ferrocenylmethyl-bis[2-{pyrid-2-yl }-ethyl]amine) contains bidentate L¹ by crystallography and NMR spectroscopy and decomposes during recrystallization from CH2-Cl2/pentane via both C-N bond cleavage and formation steps, Other [MBr2L¹] (M = Co, Ni, Cu) compounds do not undergo this reaction and contain L¹ bound in the more usual tridentate coordination mode. [ABSTRACT FROM AUTHOR]

Homochiral [M(( R )- L R ) 2 ] 2+ and heterochiral [M(( R )- L R )(( S )- L R )] 2+ isomers of [Zn( L Ph ) 2 ][BF 4 ] 2 , [Zn( L i Pr ) 2 ][BF 4 ] 2 , [Co( L Ph ) 2 ][BF 4 ] 2 , and [Co( L i Pr ) 2 ][BF 4 ] 2 ( L Ph  = 2,6- bis (4-phenyloxazolinyl)pyridine; L i Pr  = 2,6- bis (4- iso propyloxazolinyl)pyridine) have been prepared and characterised. Six of the eight compounds were crystallographically characterised, showing that steric repulsions between ligand substituents lead to more distorted coordination geometries in the homochiral isomers, especially in the L i Pr complexes. Heterochiral [M(( R )- L i Pr )(( S )- L i Pr )] 2+ (M = Zn or Co) undergoes partial racemisation in CD 3 CN through ligand redistribution reactions, whereas [M(( R )- L Ph )(( S )- L Ph )] 2+ does not (in agreement with previous reports). This may be a consequence of intramolecular π … π -interactions in [M(( R )- L Ph )(( S )- L Ph )] 2+ , whereby each pyridyl group is sandwiched between two phenyl substituents from the other L Ph ligand. These π … π -interactions are disrupted in homochiral [M(( R )- L R ) 2 ] 2+ , owing to the aforementioned steric clash between phenyl substituents in that isomer. [ABSTRACT FROM AUTHOR]

The following iron(II) complexes of 2,6- bis(oxazolinyl)pyridine (PyBox; LH) derivatives are reported: [Fe( LH)2][ClO4]2 ( 1); [Fe(( R)- LMe)2][ClO4]2 (( R)- 2; LMe=2,6- bis{4-methyloxazolinyl}pyridine); [Fe(( R)- LPh)2][ClO4]2 (( R)- 3) and [Fe(( R)- LPh)(( S)- LPh)][ClO4]2 (( RS)- 3; LPh=2,6- bis{4-phenyloxazolinyl}pyridine); and [Fe(( R)- L iPr)2][ClO4]2 (( R)- 4) and [Fe(( R)- L iPr)(( S)- L iPr)][ClO4]2 (( RS)- 4; L iPr=2,6- bis{4- isopropyloxazolinyl}pyridine). Solid ( R)- 3⋅MeNO2 exhibits an unusual very gradual, but discontinuous thermal spin-crossover with an approximate T [ABSTRACT FROM AUTHOR]

The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base-metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)2]2+ (bpp=2,6-di{pyrazol-1-yl}pyridine) can be high-spin, low-spin, or spin-crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature ( T [ABSTRACT FROM AUTHOR]

The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base-metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)2]2+ (bpp=2,6-di{pyrazol-1-yl}pyridine) can be high-spin, low-spin, or spin-crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature ( T [ABSTRACT FROM AUTHOR]

Reaction of 2,6-difluoropyridine with 2 equiv of indazole and NaH at room temperature affords a mixture of 2,6-bis(indazol-1-yl)pyridine (1-bip), 2-(indazol-1-yl)-6-(indazol-2-yl)pyridine (1,2-bip), and 2,6-bis(indazol-2-yl)pyridine (2-bip), which can be separated by solvent extraction. A two-step procedure using the same conditions also affords both 2-(indazol-1-yl)-6-(pyrazol-1-yl)pyridine (1-ipp) and 2-(indazol-2-yl)-6-(pyrazol-1-yl)pyridine (2-ipp). These are all annelated analogues of 2,6-di(pyrazol-1-yl)pyridine, an important ligand for spin-crossover complexes. Iron(II) complexes [Fe(1-bip)2]2+, [Fe(1,2-bip)2]2+, and [Fe(1-ipp)2]2+ are low-spin at room temperature, reflecting sterically imposed conformational rigidity of the 1-indazolyl ligands. In contrast, the 2-indazolyl complexes [Fe(2-bip)2]2+ and [Fe(2-ipp)2]2+ are high-spin in solution at room temperature, whereas salts of [Fe(2-bip)2]2+ exhibit thermal spin transitions in the solid state. Notably, [Fe(2-bip)2][BF4]2·2MeNO2 adopts a terpyridine embrace lattice structure and undergoes a spin transition near room temperature after annealing, resulting in thermal hysteresis that is wider than previously observed for this structure type (T1/2 = 266 K, ΔT = 16-20 K). This reflects enhanced mechanical coupling between the cations in the lattice through interdigitation of their ligand arms, which supports a previously proposed structure/function relationship for spin-crossover materials with this form of crystal packing. All of the compounds in this work exhibit blue fluorescence in solution under ambient conditions. In most cases, the ligand-based emission maxima are slightly red shifted upon complexation, but there is no detectable correlation between the emission maximum and the spin state of the iron centers. [ABSTRACT FROM AUTHOR]

Abstract: 2,6-Di(1-methyl-pyrazol-3-yl)pyridine (LMe), 2,6-di(1-allyl-pyrazol-3-yl)pyridine (LAll), 2,6-di(1-benzyl-pyrazol-3-yl)pyridine (LBz) and di(1-isopropyl-pyrazol-3-yl)pyridine (L i Pr) have been synthesized by alkylation of deprotonated di{1H-pyrazol-3-yl}pyridine (3-bpp), and converted to salts of the corresponding [Fe(LR)2]2+ complexes (R=Me, All, Bz and iPr). Crystal structures of [Fe(LMe)2]X2 (X− =BF4 −, ClO4 − and PF6 −), [Fe(LAll)2][BF4]2, [Fe(LBz)2][BF4]2 and [Fe(L i Pr)2][PF6]2 have been determined at 150K. All of these contain high-spin iron centres except [Fe(LMe)2][BF4]2·xH2O, which is predominantly low-spin at that temperature. All the complexes are high-spin between 5 and 300K as solvent-free bulk powders, and are also high-spin in (CD3)2CO solution between 193 and 293K. This was unexpected, since the parent complex [Fe(3-bpp)2]2+ undergoes spin-crossover in the same solvent with T ½ =247K [40]. The high-spin nature of the [Fe(LR)2]2+ complexes in solution must reflect a subtle balance of steric and electronic factors involving the ligand ‘R’ substituents. [Copyright &y& Elsevier]

Chlorination of 2,6-bis(pyrazol-1-yl)pyrazine (bppz) with NaClO in acetic acid afforded 2,6-bis(4-chloropyrazol-1-yl)pyrazine ( L2Cl). 2,6-Bis(4-bromopyrazol-1-yl)pyrazine ( L2Br), 2,6-bis(4-iodopyrazol-1-yl)pyrazine ( L2I), 2,6-bis(4-methylpyrazol-1-yl)pyrazine ( L2Me), and 2,6-bis(4-nitropyrazol-1-yl)pyrazine ( L2NO2) were also prepared by reactions of the preformed 4-substituted pyrazoles with 2,6-dichloropyrazine. The reduction of L2NO2 with iron powder gave 2,6-bis(4-aminopyrazol-1-yl)pyrazine ( L2NH2) and L2I was converted into 2,6-bis[4-(phenylethynyl)pyrazol-1-yl]pyrazine ( L2CCPh) by a Sonogashira coupling reaction. The salts [Fe( L2Me)2]X2 (X- = BF4- and ClO4-) underwent thermal spin-crossover abruptly at around 200 K in one and two steps, respectively. The [Fe( L2Me)2]X2 salts exhibited different light-induced excited spin-state trapping (LIESST) behavior; the BF4- salt behaves classically [ T(LIESST) = 93 K], but the ClO4- salt undergoes a multistep LIESST relaxation. In contrast, solid [Fe( L2Cl)2][BF4]2 adopts a fixed 2:1 high/low-spin-state population that does not change with temperature below 300 K, whereas [Fe( L2Br)2][BF4]2 and [Fe( L2I)2][BF4]2 form low-spin solvated crystals that are transformed into high-spin powders on drying. The pyrazinyl group in the L2R ligands slightly stabilizes the low-spin state of the complexes, as determined by solution-phase magnetic measurements. The crystal structure of [Fe( L2CCPh)(OH2) z][BF4]2 contains a disordered mixture of six- ( z = 3) and seven-coordinate ( z = 4) iron centers. [ABSTRACT FROM AUTHOR]

Presents a study which assessed the role of the H[sup +]/K[sup +]-ATPase Beta-subunit on epithelial cell development. Materials and methods; Results; Discussion.

The cover image compares the molecular spin states of two diastereomers of a spin‐crossover iron(II) complex. Solution‐phase magnetic measurements show the low‐spin state of the heterochiral (meso) diastereomer is stabilized relative to its homochiral (rac) congener. This reflects a steric clash between phenyl substituents in the rac isomer, which occupies two diagonal quadrants in the molecule. The resultant twisting of the ligand conformation and metal‐coordination sphere explains the observed reduction in the ligand field. More information can be found in the Full Paper by M. A. Halcrow et al. on page 9067. [ABSTRACT FROM AUTHOR]