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At least 253 records · Page 14Linked to original sources

What causes a crossover step when walking on uneven ground? A study in healthy young women.

We hypothesized that, during gait, the perturbation caused by stepping on a 1.2-cm high protuberance with the medial forefoot would not only alter stance foot kinematics and kinetics, but also alter subsequent step location and timing, even to the point of causing a crossover step. Twelve healthy young women performed at least three flat surface and three perturbation trials while walking along a level walkway. To obstruct visual monitoring of their upcoming foot placement they used both hands to carry a large tray in front of their abdomen. Kinematic data from optoelectronic markers and force plate data were recorded at 50 and 100Hz, respectively. The results showed that the medial forefoot perturbation significantly decreased the net ankle eversion moment (p<0.001) and increased the maximum inversional foot acceleration (p=0.007). Step width (SW) and time (ST) of the post-perturbation recovery step were significantly decreased compared with normal steps (p=0.002 and 0.049, respectively). The maximum inversional foot acceleration correlated negatively with SW and ST of the recovery step (both p=0.001). Finally, four of 36 (12%) recovery steps were crossover steps. We conclude that a medial forefoot perturbation results in an increased inversional acceleration of the stance foot followed by a decrease in recovery SW and ST. In some cases, a medial forefoot perturbation can result in a crossover step, an extreme form of a narrow recovery step.

Adult↗

Treatment crossovers did not affect randomized treatment comparisons in the Mode Selection Trial (MOST).

OBJECTIVES: We evaluated the impact of treatment crossovers on study results in the Mode Selection Trial (MOST). BACKGROUND: The MOST study, a 2,010-patient, 6-year trial comparing dual-chamber pacing (DDDR) and ventricular pacing (VVIR) in sinus node dysfunction, demonstrated no difference in death or stroke and modest reductions in heart failure hospitalization (HFH) and atrial fibrillation (AF) with DDDR pacing. However, a moderate proportion of VVIR-randomized patients were temporarily or permanently crossed over to DDDR pacing. METHODS: Intent-to-treat (ITT) analyses compared treatment arms by randomized pacing mode. On-treatment analyses used time-dependent covariates to account for all crossovers. All analyses used Cox proportional hazards models and included covariates prespecified in the study design: age, gender, Charlson index, and prior stroke, heart failure, myocardial infarction, supraventricular tachyarrhythmia, and ventricular tachycardia or fibrillation. RESULTS: Of 996 VVIR-randomized patients, 375 (38%) were DDDR paced at some time, accounting for 27% of follow-up days among all VVIR-randomized patients. Of 1,014 DDDR-randomized patients, 53 (5%) were VVIR paced at some time, accounting for 1.5% of follow-up days among all DDDR-randomized patients. On-treatment analyses showed slightly lower hazard ratios favoring DDDR versus VVIR compared with ITT: death or stroke 0.88 (on-treatment) versus 0.91 (ITT); death 0.94 versus 0.95; stroke 0.74 versus 0.81; HFH 0.72 versus 0.73; and AF 0.72 versus 0.77. Interpretation of treatment effects was unchanged. CONCLUSIONS: Although treatment crossovers accounted for >25% of follow-up time in the VVIR-randomized group, this did not affect study results. End point comparisons between randomized modes are accurate reflections of DDDR versus VVIR pacing in this study population.

Aged↗

The online case-crossover study is a novel approach to study triggers for recurrent disease flares.

OBJECTIVES: To evaluate the feasibility of conducting an online case-crossover study of triggers for recurrent disease flares. METHODS: We conducted an online case-crossover study of triggers for recurrent flares using gout as a paradigm. We constructed a Web site and recruited individuals with history of gout via the Internet. We confirmed gout diagnosis by reviewing each subject's medical records. We collected via the Internet exposure information during the intercritical period using a scheduled Control-period Questionnaire, and prior to recurrent gout attacks using a Hazard-period Questionnaire. RESULTS: Over 10 months we recruited 197 subjects with a history of gout from 41 states and the District of Columbia. We obtained medical records from 172 subjects. All participants had experienced at least one recurrent attack and filled out required questionnaires. The median time between the date of an attack and the date of logging on to the Web site was 2 days. The incidence rate of recurrent gout attacks was 1.03 per person-year. Longer disease duration and presence of comorbidities appeared to increase the risk of recurrent flares. CONCLUSION: The results of this study demonstrate that a case-crossover study can be successfully conducted through the Internet. This approach has broad applicability to other diseases typified by recurrent attacks.

Adult↗

The crossover approach to switching antipsychotics: what is the evidence?

Clinicians frequently use a crossover approach in switching antipsychotics, although historically there has been a lack of data addressing the question of switch strategies. To establish if there is now empiric evidence that may guide clinicians in this regard, a MEDLINE search to April 2004 was carried out to identify published, randomized and controlled trials that have addressed this topic. A total of 404 articles were identified in the search, which resulted in the identification of four reports meeting the criteria. The four studies evaluated switching strategies to one of three atypical antipsychotics: aripiprazole, olanzapine (two reports), and ziprasidone. The switching process itself could be subdivided as follows: discontinuation (abrupt vs. gradual); and, replacement (abrupt vs. gradual). Meta-analyses confirmed a lack of difference in outcome, regardless of approach. While a crossover approach does not appear to increase adverse events, the available empiric evidence does not support its clinical superiority on various outcome measures. The existing data therefore argue against the position that a crossover approach in switching antipsychotics represents a 'safer' means of preventing clinical deterioration during the switch.

Antipsychotic Agents↗

Hemispheric asymmetry for face recognition: cognitive style and the "crossover" effect.

Photographs of faces were serially presented for central viewing, while Ss made either "social" or "physical" judgments about each face. Subsequent tachistoscopic recognition of laterally displaced targets displayed a pattern of contrasting visual field superiorities for faces seen under the two conditions. This "crossover" pattern occurred in opposite directions for reaction time and for accuracy. Field dependent and field independent Ss displayed the crossover equally, but crossovers by field independent Ss showed a consistent direction within each dependent measure, whereas those by field dependent Ss were equally divided between the two directions. Choices of encoding strategy by field independent Ss appear to be more strongly task-determined than those by field dependent Ss, but the relation between the encoding manipulation, presumed encoding strategy differences, and specific visual field advantage remains unknown.

Adult↗

Branched chain amino acids in the treatment of latent portosystemic encephalopathy. A double-blind placebo-controlled crossover study.

Branched chain amino acids have been recommended for the treatment of portosystemic encephalopathy based on the false neurotransmitter hypothesis. This hypothesis implies that by correction of the deranged amino acid pattern in the blood of cirrhotics, false neurotransmission and then portosystemic encephalopathy is improved. We conducted a double-blind crossover placebo-controlled trial in 22 inpatients with liver cirrhosis and obtained evidence of latent (subclinical) portosystemic encephalopathy using an extensive psychometric test program. Patients received a defined diet of 35 cal/kg X day containing 1 g of protein. In addition, branched chain amino acids or casein in a dosage of 0.25 g/kg X day was administered in a crossover fashion, each for 1 wk. Semiquantitative nitrogen balance increased during both treatments, with a tendency of a larger increase during branched chain amino acid treatment. At the same time ammonia concentration tended to decrease during branched chain amino acid treatment. Taking into account the crossover design, significant improvements attributable to branched chain amino acid treatment could be demonstrated in psychomotor functions (line tracing, tapping, steadiness, auditory reaction time), attention (digit table), and practical intelligence (digit symbol, number connection test).

Adult↗

Nerve crossover techniques for urinary bladder reinnervation: animal and human cadaver studies.

Interruption of spinal pathways integrating central and peripheral bladder control mechanisms will result in neurogenic bladder dysfunction. If central pathways could be restored to the decentralized bladder through a microneural reconstructive technique a return of useful function might be achieved. This anatomical study describes the nerve crossover techniques used in human cadaver dissections for connecting intercostal nerves to sacral roots intraspinally. The techniques were modified from and compared to similar procedures used in an animal model where adjacent extradural roots were connected through a nerve graft. We have shown previously that the unilaterally decentralized bladder of the cat can be recentralized after a nerve crossover procedure. If additional laboratory studies can document return of useful bladder function we anticipate that selected patients may benefit from similar nerve crossover techniques to bypass a spinal cord lesion to recentralize the bladder.

Animals↗

Saccharomyces cerevisiae Mer3 helicase stimulates 3'-5' heteroduplex extension by Rad51; implications for crossover control in meiotic recombination.

Crossover and noncrossover recombinants can form by two different pathways during meiotic recombination in Saccharomyces cerevisiae. The MER3 gene is known to affect selectively crossover, but not noncrossover, recombination. The Mer3 protein is a DNA helicase that unwinds duplex DNA in the 3' to 5' direction. To define the underlying molecular steps of meiotic recombination, we investigated the role of Mer3 helicase in DNA strand exchange promoted by Rad51 protein. We found that Mer3 helicase does not function as an initiator of DNA pairing events but, rather, it stimulates DNA heteroduplex extension in the 3' --> 5' direction relative to the incoming (or displaced) single-stranded DNA. Conversely, Mer3 helicase blocks DNA heteroduplex extension in the 5' --> 3' direction. Our results support the idea that Mer3 helicase stabilizes nascent joint molecules via DNA heteroduplex extension to permit capture of the second processed end of a double-stranded DNA break, a step which is required for crossover recombinant product formation.

DNA↗

Assessment of average, population and individual bioequivalence in two- and four-period crossover studies.

The aim of bioequivalence studies is to assess the equivalence of two pharmaceutical formulations of the same active drug substance. Currently three types of bioequivalence are distinguished: average, population and individual bioequivalence. Average and population bioequivalence can be assessed in two-period (non-replicated) crossover studies, whereas individual bioequivalence requires three- or four-period replicated studies, with a preference for four-period studies. The PC-program BIOEQV80 is presented for the statistical analysis of average and population bioequivalence from two-period crossover studies. The program BIOEQ2X2 is presented for the statistical analysis of all three types of bioequivalence from four-period replicated crossover studies. The statistical aspects of population and individual bioequivalence are based on a recent Guidance issued by the US Food and Drug Administration.

Cross-Over Studies↗

A randomized, double-blind, placebo-controlled, crossover study to assess the immediate effect of sublingual glyceryl trinitrate on the ankle brachial pressure index, claudication, and maximum walking distance of patients with intermittent claudication.

PURPOSE: The goal of the present study was to assess the immediate effect of sublingual glyceryl trinitrate (GTN) in patients with intermittent claudication. METHODS: We conducted a randomized, double-blind, placebo-controlled crossover study. Inclusion criteria consisted of history of intermittent claudication, resting ankle brachial pressure index (ABPI) of 1.00 or less, a 20% or greater fall in ABPI after exercise, and maximum walking distance (MWD) of less than 250 m. Patients already receiving nitrates were excluded. In study 1, patients (n = 25) underwent a standard exercise test after randomization to receive either 800 microg of sublingual GTN or placebo. The postexercise ABPI was recorded. Then, the crossover portion of the study was performed. In study 2, patients (n = 22) had their claudication distance and MWD measured. They then were randomized to receive either GTN or placebo spray, and the exercise test was repeated, with the claudication distance and MWD recorded, followed by the crossover portion of the study. Statistical analysis was performed with the Wilcoxon matched pairs signed ranks test and the Mann-Whitney U test. RESULTS: In study 1, the median postexercise ABPIs for placebo and GTN were 0.29 and 0.36 (P =.0001). In study 2, the median claudication distance for both placebo and GTN groups was 70 m (P =.59). The median MWD for the placebo and GTN groups was 105 and 125 m (P =.0084) CONCLUSION: GTN can decrease the fall in ABPI after exercise and increase the MWD.

Administration, Sublingual↗

Docetaxel compared with sequential methotrexate and 5-fluorouracil in patients with advanced breast cancer after anthracycline failure: a randomised phase III study with crossover on progression by the Scandinavian Breast Group.

The aim of this study was to compare the efficacy and tolerability of docetaxel to methotrexate and 5-fluorouracil in advanced breast cancer after anthracycline failure. A randomised multicentre trial was conducted in 283 patients with advanced breast cancer who had failed previous anthracycline treatment. Docetaxel at a dose of 100 mg/m2 every 3 weeks (n = 143) was compared with sequential methotrexate and 5-fluorouracil (MF; n = 139) given at day 1 and 8 every 3 weeks at dosages of 200 mg/ m2 and 600 mg/m2, respectively. After progression, crossover to the alternative treatment group was recommended. There was a significantly higher overall response rate in the docetaxel 42% (CR 8% + PR 34%) than in the MF arm 21% (CR 3% + PR 18%) (P < 0.001). The median time to progression (TTP) was 6.3 months in the docetaxel arm and 3.0 months in the MF arm (P < 0.001). Docetaxel also had a significantly higher response rate of 27% following crossover compared with MF (12%). Significantly more side-effects (leucopenia, infections, neuropathy, oedema, asthenia, skin, nail changes, alopecia) were seen in the docetaxel than in the MF group. However, grade 3 and 4 side-effects were infrequent with both drugs, with the exception of fatigue, alopecia and infections. Median overall survival (OS) including crossover phase was 10.4 months in the docetaxel and 11.1 months in the MF arm (P = 0.79). Based on the response rate and the primary endpoint of TTP, docetaxel is superior to sequential methotrexate and 5-fluorouracil in advanced breast cancer after anthracycline failure.

Adult↗

Femorofemoral crossover grafts for claudication: a safe and reliable procedure.

OBJECTIVE: To evaluate the role of femorofemoral crossover grafts in patients with disabling claudication. DESIGN: Retrospective study. SETTING: University hospital. MATERIALS: Two hundred and eleven patients with iliac artery disease undergoing femorofemoral crossover grafts for disabling claudication. CHIEF OUTCOME MEASURES: Perioperative mortality, follow-up cumulative graft patency, limb loss, survival, graft infection and false aneurysm formation were evaluated to determine the immediate and long-term outcome of the procedure. MAIN RESULTS: Primary and secondary graft patency at 5 years was 72% and 89% respectively. There were no perioperative deaths (zero 30 day mortality). Dacron was used in 66 patients (31%) and PTFE in 145 (69%). There were no differences in patency between the two graft materials but eight Dacron grafts (12.1%) were removed because of complications (false aneurysm or infection) compared to four PTFE grafts (2.7%) (p < 0.001 Chi-square). Five patients (2%) have undergone a major lower limb amputation. Forty-one patients (19%) have required subsequent inflow procedures which represents a cumulative need for inflow of 5% per year. CONCLUSIONS: Femorofemoral crossover grafts are a safe and reliable procedure in patients with disabling claudication caused by unilateral iliac artery disease.

Adult↗

Splitter imperfections in annular split-flow thin separation channels: effect on nonspecific crossover.

The separation performance of split-flow thin (SPLITT) separation channels generally falls short of ideal behavior. There are many possible contributing factors to the loss of separation resolution, and these are discussed in the text. The possibility that small imperfections in the splitters play a significant role is examined in this study. Computational fluid dynamics is used to determine the flow pattern within an annular SPLITT channel having small imperfections in the inlet splitter. These results are used to calculate the nonspecific crossover of particles from the inner annular inlet to the outer annular outlet under various flow rate regimes. Nonspecific crossover, obtained through convective transport alone, and not the result of field-induced transport, is often used as a check of channel behavior. The results of a typical experimental determination of nonspecific crossover are included for comparison. It is concluded that geometrical imperfections can indeed play a significant role in the loss of resolution observed for these systems.

Cell Separation↗

A high-pressure iron K-edge x-ray absorption spectral study of the spin-state crossover in (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))I(2) and (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))(BF(4))(2).

The room temperature iron K-edge X-ray absorption near edge structure spectra of (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))I(2) and (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))(BF(4))(2) have been measured between ambient and 88 and 94 kbar, respectively, in an opposed diamond anvil cell. The iron(II) in (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))I(2)undergoes the expected gradual spin-state crossover from the high-spin state to the low-spin state with increasing pressure. In contrast, the iron(II) in (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))(BF(4))(2) remains high-spin between ambient and 78 kbar and is only transformed to the low-spin state at an applied pressure of between 78 and 94 kbar. No visible change is observed in the preedge peak in the spectra of (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))I(2) with increasing pressure, whereas the preedge peak in the spectra of ((e[HC(3,5-(CH(3))(2)pz)(3)](2))(BF(4))(2) changes as expected for a high-spin to low-spin crossover with increasing pressure. The difference in the spin-state crossover behavior of these two complexes is likely related to the unusual behavior of (Fe[HC(3,5-(CH(3))(2)pz)(3)](2))(BF(4))(2) upon cooling.

Journal Article↗

S = (3)/(2) <= => S = (1)/(2) spin crossover behavior in five-coordinate halido- and pseudohalido-bis(o-iminobenzosemiquinonato)iron(III) complexes.

Five-coordinate halido- and pseudohalido-bis(o-iminobenzosemiquinonato)iron(III) complexes [Fe(III)X(L(ISQ))(2)] (X = Cl(-) (1), Br(-) (2a, 2b), I(-) (3), N(3)(-) (4), and NCS(-) (5)) have been synthesized where (L(ISQ))(1)(*)(-) represents the pi radical anion N-phenyl-o-imino(4,6-di-tert-butyl)benzosemiquinonate(1-). The molecular structures of the two polymorphs 2a and 2b have been determined at 100, 220, and 295 K, respectively, by single crystal X-ray crystallography. Variable temperature magnetic susceptibility data reveal the following electronic ground states, S(t): For 1, it is (3)/(2). Polymorph 2a contains a 1:1 mixture of (3)/(2) and (1)/(2) forms in the range 4.2 to approximately 150 K; above 150 K the latter form undergoes a spin crossover (1)/(2) --> (3)/(2). Polymorph 2b contains only the S(t) = (3)/(2) form (4-300 K). Complex 3 contains the S(t) = (1)/(2) form in the range 4-130 K, but above 130 K, a spin crossover to the (3)/(2) form is observed which is confirmed by three crystal structure determinations at 100, 220, and 295 K. Complex 4 possesses an S(t) = (1)/(2) ground state at 80 K and undergoes a spin crossover at higher temperatures. Complex 5 has a temperature-independent S(t) = (3)/(2) ground state. All crystal structures of 1, 2a, 2b, 3, 4, and 5, regardless at which temperature the data sets have been measured, show that two o-iminobenzosemiquinonate(1-) pi radical anions are N,O-coordinated in all of these neutral iron complexes. The Fe-N and Fe-O bond distances are longer in the S(t) = (3)/(2) and shorter in the S(t) = (1)/(2) forms. The S(t) = (3)/(2) ground state is attained via intramolecular antiferromagnetic coupling between a high spin ferric ion (S(Fe) = (5)/(2)) and two ligand pi radicals whereas the S(t) = (1)/(2) form is generated from exchange coupling between an intermediate spin ferric ion (S(Fe) = (3)/(2)) and two ligand radicals.

Journal Article↗

Interlayer interaction of two-dimensional layered spin crossover complexes [FeIIH3L(Me)][FeIIL(Me)]X (X-=ClO4-, BF4-, PF6-, AsF6-, and SbF6-; H3L(Me)=tris[2-(((2-methylimidazol-4-yl)methylidene)amino)ethyl]amine).

A series of two-dimensional (2D) spin crossover complexes, [FeIIH3L(Me)][FeIIL(Me)]X (X-=ClO4-, BF4-, PF6-, AsF6-, SbF6-) 1-5, have been synthesized, where H3L(Me) denotes an hexadentate N6 tripodlike ligand containing three imidazole groups, tris[2-(((2-methylimidazol-4-yl)methylidene)amino)ethyl]amine. Compounds 1-5 exhibit a two-step (HS-[FeIIH3L(Me)](2+) + HS-[FeIIL(Me)]-) <--> (HS-[FeIIH3L(Me)](2+) + LS-[FeIIL(Me)]-) <--> (LS-[FeIIH3L(Me)](2+) + LS-[FeIIL(Me)]-) spin-transition. The crystal structure of [FeIIH3L(Me)][FeIIL(Me)]PF6 (3) was determined at 295, 200, and 100 K. The structure consists of homochiral extended 2D puckered sheets, in which the complementary [FeIIH3L(Me)](2+) and [FeIIL(Me)]- capped tripodlike components, linked together by imidazole-imidazolate hydrogen bonds, are alternately arrayed in an up-and-down mode. The Fe-N bond distances and angles revealed that the FeII sites of both constituting units are in the high-spin (HS) state at 295 K; at 200 K, the FeII sites of [FeIIH3L(Me)](2+) and [FeIIL(Me)]- are in the HS and low-spin (LS) states, respectively. The FeII sites of both constituting units are in the LS state at 100 K. The size of the counteranion affects significantly the intra- and interlayer interactions leading to modifications of the spin crossover behavior. The onset of the second spin-transition of the ClO4- (1) and BF4- (2) salts adjoins the first spin-transition, while a mixed (HS-[FeIIH3L(Me)](2+) + LS-[FeIIL(Me)]-) spin-state spans a temperature range as wide as 70 K for salts 3-5 with larger counteranions, PF6-, AsF6-, and SbF6-, respectively. Compounds 1 and 2 showed remarkable LIESST (light induced excited spin state trapping) and reverse-LIESST effects, whereas 3-5 showed no remarkable LIESST effect. The interlayer interaction due to the size of the counteranion is an important factor governing the spin crossover behavior and LIESST effect.

Journal Article↗

Molecular structure and vibrational spectra of spin-crossover complexes in solution and colloidal media: resonance Raman and time-resolved resonance Raman studies.

The spin-crossover system [Fe(btpa)](PF(6))(2) (btpa = N,N,N',N'-tetrakis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) and the predominantly low-spin species [Fe(b(bdpa))](PF(6))(2) ((b(bdpa) = N,N'-bis(benzyl)-N,N'-bis(2-pyridylmethyl)-6,6'-bis(aminomethyl)-2,2'-bipyridine) have been characterized by means of X-ray diffraction. The unit cell of [Fe(btpa)](PF(6))(2) contains two crystallographically independent molecules revealing octahedral low-spin and quasi-seven-coordinated high-spin structures. The unit cell of [Fe(b(bdpa))](PF(6))(2) contains two crystallographically independent molecules one of which corresponds to a low-spin structure, while the other reveals a disordering. On the basis of magnetic susceptibility and Mössbauer measurements, it has been proposed that this disorder involves low-spin and high-spin six-coordinated molecules. The structures of [Zn(btpa)](PF(6))(2) and [Ru(btpa)](PF(6))(2) have been determined also. Pulsed laser photoperturbation, coupled here with time-resolved resonance Raman spectroscopy (TR(3)), has been used to investigate, for the first time by this technique, the relaxation dynamics in solution on nanosecond and picosecond time scales of low-spin, LS ((1)A) --> high-spin, HS ((5)T) electronic spin-state crossover in these Fe(II) complexes. For the nanosecond experiments, use of a probe wavelength at 321 nm, falling within the pi-pi transition of the polypyridyl backbone of the ligands, enabled the investigation of vibrational modes of both LS and HS isomers, through coupling to spin-state-dependent angle changes of the backbone. Supplementary investigations of the spin-crossover (SCO) equilibrium in homogeneous solution and in colloidal media assisted the assignment of prominent features in the Raman spectra of the LS and HS isomers. The relaxation data from the nanosecond studies confirm and extend earlier spectrophotometric findings, (Schenker, S.; Stein, P. C.; Wolny, J. A.; Brady, C.; McGarvey, J. J.; Toftlund, H.; Hauser, A. Inorg. Chem. 2001, 40, 134), pointing to biphasic spin-state relaxation in the case of [Fe(btpa)](PF(6))(2) but monophasic in the case of [Fe(b(bdpa))](PF(6))(2). The picosecond results suggest an early process complete in 20 ps or less, which is common to both complexes and possibly includes vibrational relaxation in the initially formed (5)T(2) state.

Journal Article↗

Structural and Kinetic Studies of Spin Crossover in an Iron(II) Complex with a Novel Tripodal Ligand.

Configurational and ligand conformational influences on the kinetics of (1)A(1) right harpoon over left harpoon (5)T(2) spin crossover in the Fe(II) complex with the novel tripodal ligand, 1,1,1-tris((N-(2-pyridylmethyl)-N-methylamino)methyl)ethane (tptMetame), have been explored. Despite having six chelate rings and three chiral nitrogen atoms, only one enantiomeric pair of isomers, Delta, SSS, and Lambda, RRR, of the complex ion is observed. The conformation of the three rings forming the upper "cap" of the complex structure can be assigned delta or lambda with respect to the 3-fold molecular axis. X-ray data at 300 and 153 K, above and below the critical temperature for the spin transition, show that the conformation of the ligand "cap" is the same as the absolute configuration of the complex, with the same Lambdalambda(CAP)(or Deltadelta(CAP)) combination prevailing for both the LS ((1)A(1)) and HS ((5)T(2)) isomers. Molecular mechanics calculations further show that the ligand energy remains lowest for this Lambdalambda(CAP) (or Deltadelta(CAP)) combination at all Fe-N distances over the range spanning the LS and HS isomers. Measurements of the spin crossover relaxation time have been carried out in solution over the temperature range 293-170 K. The observed monophasic relaxation traces are also consistent with the absolute configuration of the complex remaining unaltered during the spin crossover.

Journal Article↗