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Heteronucleard-dandd-fRu(II)/Mcomplexes[M=Gd(III),Yb(III),Nd(III),Zn(II)orMn(II)]ofligandscombiningphenanthrolineandaminocarboxylatebindingsites:combinedrelaxivity,cellimagingandphotophysicalstudies.

BethanyJ.Crowston,JamesD.Shipp,DimitriChekulaev,LukeK.McKenzie,CallumJones,JuliaA.Weinstein,AnthonyJ.H.Meijer,HelenE.Bryant,LouiseNatrajan,AdamWoodwardandMichaelD.Ward*

ExperimentalSupportingInformation

mmmmcccc

Fig.S1.1HNMRspectrum(400MHz,d6-acetone)ofRu•E.Hb=Protononbipyridineligand;Hp

=protononphenanthrolineligand;Hpy=protononpyridinering.

Fig.S2.High-resolutionESmassspectrumofRu•E

Hb

Hpy

HbHbHpHbHb

HbHb

Hb

Hp

HpHpHb/Hp

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019

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Fig.S3.1HNMRspectrum(500MHz,d6-DMSO)ofRu•L.Hb=Protononbipyridineligand;Hp=protononphenanthrolineligand;Hpy=protononpyridinering.

Fig.S4.High-resolutionESmassspectrumofRu•L

Hp

Hpy

HbHbHbHb/HpHbHp HbHbHpHpHp

Hb/Hp

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Fig.S5.1HNMRspectrum(400MHz,d6-acetone)ofRu•E2at298K.Hb=protononbipyridineligand,Hp=protononphenanthrolineligand,Hpy=protononpyridinering.

Fig.S6High-resolutionESmassspectrumofRu•E2

Hpy

HbHbHbHb

Hb

HpHpHbHp

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Fig.S7.1HNMRspectrum(400MHz,D2O)ofRu•L2at298K.Hb=protononbipyridineligand,Hp=protononphenanthrolineligand,Hpy=protononpyridinering.

Fig.S8.High-resolutionESmassspectrumofRu•L2

HbHbHb

Hpy

HpHp

HpHbHbHb

Hb

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Fig.S9.Partofthehigh-resolutionESmassspectrumofRu•Gdshowing(top)observedand(below)calculatedsignalsfor[C49H37N9O8RuGd+H]2+

Fig.S10.Partofthehigh-resolutionESmassspectrumofRu•Gd2showing(top)observedand(bottom)calculatedsignalsfor[C66H50N12O16RuGd2+2H]2+

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Fig.S11.PartofthehighresolutionESmassspectrumofRu•Ndshowingthesignalfor[C49H37N9O8RuNd+H]2+.

Fig.S12.PartofthehighresolutionESmassspectrumofRu•Ybshowingthesignalfor[C49H37N9O8RuYb+H]2+.

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Fig.S13.PartofthehighresolutionESmassspectrumofRu•Nd2showingthesignalfor[C66H50N12O16RuNd2+2H]2+.

Fig.S14.PartofthehighresolutionESmassspectrumofRu•Yb2showingthesignalfor[C66H50N12O16RuYb2+2H]2+.

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Fig.S15.1HNMRspectrum(400MHz,D2O)ofRu•Znat298K.(Hb=protononbipyridineligand,Hp=protononphenanthrolineligand,Hpy=protononpyridinering).

Fig.S16.PartofthehighresolutionESmassspectrumofRu•Znshowingthesignalfor[C49H37N9O8RuZn+2H]2+.

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Fig.S17.PartofthehighresolutionESmassspectrumofRu•Mnshowingthesignalfor[C49H37N9O8RuMn+2H]2+.

Fig.S18.1HNMRspectrum(400MHz,D2O)ofRu•Zn2at298K.(Hb=protononbipyridineligand,Hp=protononphenanthrolineligand,Hpy=protononpyridinering).

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Fig.S19.PartofthehighresolutionESmassspectrumofRu•Zn2showingthesignalfor[C66H50N12O16RuZn2]2-.

Fig.S20.PartofthehighresolutionESmassspectrumofRu•Mn2showingthesignalfor[C66H50N12O16RuMn2]2-.

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Fig.S21.UV/VisabsorptionspectrainMeOH,normalisedat435nm,ofRu•E(green)andRu•E2(red),emphasisingthedifferenceinthe1MLCTabsorptionregion(500–550nm).Forextinctioncoefficientsseemaintext.

Fig.S22.ExcitationspectrarecordedinD2Oat298Kof(a)Ru•Ndand(b)Ru•Nd2,monitoringexcitationat1060nminbothcases,showingoverlapofthemainfeatureoftheexcitationspectrawiththeRu-based1MLCTabsorptionmanifold.

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Fig.S23.Decay-associatedspectraobtainedbyglobalanalysisofthetransientabsorptionspectraldataofRu•Zn(left)andRu•Mn,inwateratRT.

Fig.S24.Evolution-associatedspectra,illustratingtheappearanceoftheexperimentalTAspectraatdifferenttimedelays,forRu•Zn(left)andRu•Mn(right),inwateratRT.

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Fig.S25.Plotofrelaxationrateofwaterprotons(s-1)vs.concentrationofGd(III)-containingcomplex(mM)forRu•Gd(reddots),Ru•Gd2(bluedots)andMagnevist(greendots)(400MHz,298K,D2O).

Fig.S26.ClonogenictoxicityassayofHeLacellsincubatedwithRu•Gd(redline)orRu•Gd2(blueline)atconcentrationsof50µMand200µMfor4h.IncubationswerecarriedoutinfullDMEDat37˚CunderanatmosphereofCO2/air(5/95,v/v)for7–10daysuntilvisiblecellcolonieshadformed.Errorbarsrepresentthestandarddeviationofsixdatapoints(three

repeatsofeachofduplicatedatasets).

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Fig.S27.Plotofconcentration(mM)vs.relaxationrateofwaterprotons(s-1)todeterminetheconcentration-normalisedlongitudinalrelaxivityvaluesforRu•Mn(orange)andRu•Mn2(purple).ThedataforRu•Gd(red),andRu•Gd2(blue)andthecommercialMRIcontrastagentMagnevist®(green)arealsoincludedforcomparison(400MHz,298K,D2O).